U.S. patent application number 13/817660 was filed with the patent office on 2013-06-13 for emulsions containing saccharide siloxane copolymer emulsifiers and methods for their preparation and use.
This patent application is currently assigned to DOW CORNING CORPORATION. The applicant listed for this patent is Cindy Delvalle, Eric Jude Joffre, Cinecttina Scavuzzo, Simon Toth, Isabelle Van Reeth. Invention is credited to Cindy Delvalle, Eric Jude Joffre, Cinecttina Scavuzzo, Simon Toth, Isabelle Van Reeth.
Application Number | 20130149260 13/817660 |
Document ID | / |
Family ID | 45723740 |
Filed Date | 2013-06-13 |
United States Patent
Application |
20130149260 |
Kind Code |
A1 |
Delvalle; Cindy ; et
al. |
June 13, 2013 |
EMULSIONS CONTAINING SACCHARIDE SILOXANE COPOLYMER EMULSIFIERS AND
METHODS FOR THEIR PREPARATION AND USE
Abstract
An emulsion contains a saccharide siloxane copolymer as an
emulsifier. The emulsion is useful in formulating personal care
products.
Inventors: |
Delvalle; Cindy; (Uccle,
BE) ; Joffre; Eric Jude; (Midland, MI) ;
Scavuzzo; Cinecttina; (Chap.-Lez-Herlaimont, BE) ;
Toth; Simon; (Midland, MI) ; Van Reeth; Isabelle;
(Shanghai, CN) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Delvalle; Cindy
Joffre; Eric Jude
Scavuzzo; Cinecttina
Toth; Simon
Van Reeth; Isabelle |
Uccle
Midland
Chap.-Lez-Herlaimont
Midland
Shanghai |
MI
MI |
BE
US
BE
US
CN |
|
|
Assignee: |
DOW CORNING CORPORATION
MIDLAND
MI
|
Family ID: |
45723740 |
Appl. No.: |
13/817660 |
Filed: |
August 15, 2011 |
PCT Filed: |
August 15, 2011 |
PCT NO: |
PCT/US11/47718 |
371 Date: |
February 19, 2013 |
Current U.S.
Class: |
424/49 ; 424/59;
424/61; 424/63; 424/64; 424/65; 424/70.1; 424/70.6; 424/70.7;
424/73; 510/417; 512/1; 512/10; 512/11; 512/25; 512/27; 514/777;
536/1.11; 536/124; 8/161 |
Current CPC
Class: |
A61Q 5/12 20130101; A61Q
5/02 20130101; A61Q 11/00 20130101; A61Q 1/02 20130101; A61Q 13/00
20130101; C08G 77/26 20130101; A61K 8/898 20130101; A61Q 5/06
20130101; A61K 2800/10 20130101; C08G 77/388 20130101; A61Q 9/00
20130101; C08G 77/16 20130101; A61Q 5/065 20130101; A61K 8/73
20130101; A61Q 15/00 20130101; A61K 8/06 20130101; A61Q 1/06
20130101; A61Q 3/00 20130101; A61Q 17/04 20130101; A61Q 1/10
20130101; C08G 77/42 20130101; A61Q 19/00 20130101 |
Class at
Publication: |
424/49 ; 514/777;
424/70.1; 424/63; 424/61; 424/59; 424/65; 424/70.6; 424/73;
424/70.7; 424/64; 536/1.11; 536/124; 512/1; 510/417; 512/25;
512/10; 512/27; 512/11; 8/161 |
International
Class: |
A61K 8/73 20060101
A61K008/73; A61Q 1/02 20060101 A61Q001/02; A61Q 3/00 20060101
A61Q003/00; A61Q 17/04 20060101 A61Q017/04; A61Q 15/00 20060101
A61Q015/00; A61Q 9/00 20060101 A61Q009/00; A61Q 19/00 20060101
A61Q019/00; A61Q 1/10 20060101 A61Q001/10; A61Q 1/06 20060101
A61Q001/06; A61Q 11/00 20060101 A61Q011/00; A61Q 5/02 20060101
A61Q005/02; A61Q 13/00 20060101 A61Q013/00; A61Q 5/12 20060101
A61Q005/12; A61Q 5/06 20060101 A61Q005/06 |
Foreign Application Data
Date |
Code |
Application Number |
Aug 23, 2010 |
US |
61375938 |
Oct 29, 2010 |
US |
61407981 |
Claims
1. An emulsion comprising: A) an aqueous phase, B) an oil phase,
and C) an emulsifier, where the emulsifier is a saccharide siloxane
copolymer of formula:
R.sup.2.sub.aR.sup.1.sub.(3-a)SiO--[(SiR.sup.2R.sup.1O).sub.m---
(SiR.sup.1.sub.2O).sub.n].sub.y--SiR.sup.1.sub.(3-a)R.sup.2.sub.a;
where each R.sup.1 can be the same or different and each R.sup.1
comprises hydrogen, an alkyl group, an organic group, or a group of
formula R.sup.3-Q; Q comprises an epoxy, cycloalkylepoxy, primary
or secondary amino, ethylenediamine, carboxy, halogen, vinyl,
allyl, anhydride, or mercapto functionality; subscripts m and n are
integers from 0 to 15,000 and may be the same or different; each
subscript a is independently 0, 1, 2, or 3; subscript y is an
integer such that the copolymer has a molecular weight less than 1
million; each R.sup.2 has formula
Z-(G.sup.1).sub.b-(G.sup.2).sub.c, and there is an average of at
least one R.sup.2 per copolymer molecule, where G.sup.1 is a
saccharide component comprising 5 to 12 carbon atoms, a quantity
(b+c) has a value ranging from 1 to 10, and subscript b or
subscript c can be 0, G.sup.2 is a saccharide component comprising
5 to 12 carbon atoms additionally substituted with organic or
organosilicon radicals, each Z is a linking group and is
independently selected from the group consisting of:
--R.sup.3--N(R.sup.8)--C(O)--R.sup.4--,
--R.sup.3--CH(OH)--CH.sub.2--N(R.sup.8)--R.sup.4--, or
--R.sup.3--CH(N(R.sup.4)(R.sup.8))CH.sub.2OH; where each R.sup.3
and each R.sup.4 are divalent spacer groups comprising a group of
formula (R.sup.5).sub.r(R.sup.6).sub.s(R.sup.7).sub.t, where at
least one of subscripts r, s and t is 1, and each R.sup.5 and each
R.sup.7 are independently either an alkylene group of 1 to 12
carbon atoms or a group of formula (R.sup.9O).sub.p, where
subscript p is an integer with a value ranging from 1 to 50, and
each R.sup.9 is a divalent organic group, and each R.sup.9O may be
the same or different, each R.sup.6 is --N(R.sup.8)--, where
R.sup.8 is selected from R.sup.3, a group of formula Z--X, a
monovalent hydrocarbon group, or a reaction product of --N(H)--
with an epoxy functional group, a cycloalkylepoxy functional group,
a glycidyl ether functional group, an acid anhydride functional
group, or a lactone; each X is independently a divalent a
carboxylic acid, phosphate, sulfate, sulfonate or quaternary
ammonium radical, and with the proviso that each R.sup.3 and each
R.sup.4 may be the same or different.
2. The emulsion of claim 1, where the aqueous phase is
discontinuous and the oil phase is continuous.
3. The emulsion of claim 1 or claim 2, where the oil phase
comprises a silicone oil.
4. The emulsion of claim 3, where the silicone oil is a
polydialkylsiloxane.
5. The emulsion of claim 1 or claim 2, where the oil is an organic
oil selected from a hydrocarbon oil, an ester, a vegetable oil, a
mineral oil, or a fatty alcohol.
6. The emulsion of claim 1, where the copolymer and the oil are
present in an amounts such that a weight ratio of copolymer/oil
ranges from 1/1 to 1/50.
7. A composition comprising: (A) the emulsion according to any one
of claims 1 to 6, and (B) an additional ingredient.
8. The composition of claim 7, where ingredient (B) is selected
from: additional silicones, aerosols, anti-oxidants, cleansing
agents, colorants, additional conditioning agents, deposition
agents, electrolytes, emollients and oils, exfoliating agents, foam
boosters, fragrances, humectants, occlusive agents, pediculicides,
pH control agents, pigments, preservatives, biocides, other
solvents, stabilizers, sunscreening agents, suspending agents,
tanning agents, other surfactants, thickeners, vitamins,
botanicals, waxes, rheology-modifying agents, antiperspirants,
anti-dandruff, anti-acne, anti-carie and wound healing-promotion
agents, an additional oil, a hydrophilic medium, a filler, a fiber,
a film forming polymer, an additional surfactant and/or emulsifier,
a dyestuff, a structuring agent, an active ingredient, a fragrance,
a preservative, and combinations thereof.
9. A composition according to claim 7 or claim 8, where the
composition is a personal care composition adapted to provide a
benefit to the a portion of the body to which it is applied.
10. The composition of claim 9, where the personal care composition
is selected from antiperspirants and deodorants, skin creams, skin
care lotions, moisturizers, facial treatments such as acne or
wrinkle removers, personal and facial cleansers, bath oils,
perfumes, colognes, sachets, sunscreens, pre-shave and after-shave
lotions, shaving soaps, and shaving lathers, hair shampoos, hair
conditioners, hair colorants, hair relaxants, hair sprays, mousses,
gels, permanents, depilatories, and cuticle coats, make-ups, color
cosmetics, foundations, concealers, blushes, lipsticks, eyeliners,
mascara, oil removers, color cosmetic removers, wrinkle fillers,
skin imperfection hiders, skin surface smoothers, eyelash curlers,
nail varnishes, hair make-up products, eye shadows, body makeups,
and powders, medicament creams, pastes or sprays including
anti-acne, dental hygienic, antibiotic, healing promotive,
nutritive and the like, which may be preventative and/or
therapeutic.
11. A method of making the emulsion of any one of claims 1 to 6,
comprising: 1) dispersing the copolymer in the oil, 2) adding the
aqueous phase to the product of step 1), and 3) mixing.
12. The method of claim 11, where the method further comprises
subjecting the emulsion to shear during and/or after step 2).
13. The method of claim 11, where step 2) and step 3) are performed
incrementally by adding a portion of the aqueous phase, mixing, and
thereafter repeating until all of the aqueous phase is added.
14. A saccharide siloxane copolymer of formula:
R.sup.2.sub.aR.sup.1.sub.(3-a)SiO--[(SiR.sup.2R.sup.1O).sub.m--(SiR.sup.1-
.sub.2O).sub.n].sub.y--SiR.sup.1.sub.(3-a)R.sup.2.sub.a; where each
R.sup.1 can be the same or different and each R.sup.1 comprises
hydrogen, an alkyl group, an organic group, or a group of formula
R.sup.3-Q; Q comprises an epoxy, cycloalkylepoxy, primary or
secondary amino, ethylenediamine, carboxy, halogen, vinyl, allyl,
anhydride, or mercapto functionality; subscripts m and n are
integers from 0 to 500 and may be the same or different; each
subscript a is independently 0, 1, 2, or 3; subscript y is an
integer such that the copolymer has a molecular weight less than 1
million; each R.sup.2 has formula
Z-(G.sup.1).sub.b-(G.sup.2).sub.c, and there is an average of at
least one R.sup.2 per copolymer molecule, where G.sup.1 is a
saccharide component comprising 5 to 12 carbon atoms, a quantity
(b+c) has a value ranging from 1 to 10, and subscript b or
subscript c can be 0, G.sup.2 is a saccharide component comprising
5 to 12 carbon atoms additionally substituted with organic or
organosilicon radicals, each Z is a linking group and is
independently selected from the group consisting of:
--R.sup.3--N(R.sup.8)--C(O)--R.sup.4--,
--R.sup.3--CH(OH)--CH.sub.2--N(R.sup.8)--R.sup.4--, or
--R.sup.3--CH(N(R.sup.4)(R.sup.8))CH.sub.2OH; where each R.sup.3
and each R.sup.4 are divalent spacer groups comprising a group of
formula (R.sup.5).sub.r(R.sup.6).sub.s(R.sup.7).sub.t, where at
least one of subscripts r, s and t is 1, and each R.sup.5 and each
R.sup.7 are independently either an alkylene group of 1 to 12
carbon atoms or a group of formula (R.sup.9O).sub.p, where
subscript p is an integer with a value ranging from 1 to 50, and
each R.sup.9 is a divalent organic group, and each R.sup.9O may be
the same or different, each R.sup.6 is --N(R.sup.8)--, where
R.sup.8 is selected from R.sup.3, a group of formula Z--X, a
monovalent hydrocarbon group, or a reaction product of --N(H)--
with an epoxy functional group, a cycloalkylepoxy functional group,
a glycidyl ether functional group, an acid anhydride functional
group, or a lactone; each X is independently a divalent a
carboxylic acid, phosphate, sulfate, sulfonate or quaternary
ammonium radical, and with the proviso that each R.sup.3 and each
R.sup.4 may be the same or different.
15. The copolymer of claim 14, where each R.sup.5 and each R.sup.7
are independently an alkylene group of 1 to 12 carbon atoms.
16. A method of making a copolymer of formula:
R.sup.2.sub.aR.sup.1.sub.(3-a)SiO--[(SiR.sup.2R.sup.1O).sub.m--(SiR.sup.1-
.sub.2O).sub.n].sub.y--SiR.sup.1.sub.(3-a)R.sup.2.sub.a; where each
R.sup.1 can be the same or different and each R.sup.1 comprises
hydrogen, an alkyl group, an organic group, or a group of formula
R.sup.3-Q; Q comprises an epoxy, cycloalkylepoxy, primary or
secondary amino, ethylenediamine, carboxy, halogen, vinyl, allyl,
anhydride, or mercapto functionality; subscripts m and n are
integers from 0 to 10,000 and may be the same or different; each
subscript a is independently 0, 1, 2, or 3; subscript y is an
integer such that the copolymer has a molecular weight less than 1
million; each R.sup.2 has formula
Z-(G.sup.1).sub.b-(G.sup.2).sub.c, and there is an average of at
least one R.sup.2 per copolymer molecule, where G.sup.1 is a
saccharide component comprising 5 to 12 carbon atoms, a quantity
(b+c) has a value ranging from 1 to 10, and subscript b or
subscript c can be 0, G.sup.2 is a saccharide component comprising
5 to 12 carbon atoms additionally substituted with organic or
organosilicon radicals, each Z is a linking group and is
independently selected from the group consisting of:
--R.sup.3--N(R.sup.8)--C(O)--R.sup.4--,
--R.sup.3--CH(OH)--CH.sub.2--N(R.sup.8)--R.sup.4--, or
--R.sup.3--CH(N(R.sup.4)(R.sup.8))CH.sub.2OH; where each R.sup.3
and each R.sup.4 are divalent spacer groups comprising a group of
formula (R.sup.5).sub.r(R.sup.6).sub.s(R.sup.7).sub.t, where at
least one of subscripts r, s and t is 1, and each R.sup.5 and each
R.sup.7 are independently either an alkylene group of 1 to 12
carbon atoms or a group of formula (R.sup.9O).sub.p, where
subscript p is an integer with a value ranging from 1 to 50, and
each R.sup.9 is a divalent organic group, and each R.sup.9O may be
the same or different, each R.sup.6 is --N(R.sup.8)--, where
R.sup.8 is selected from R.sup.3, a group of formula Z--X, a
monovalent hydrocarbon group, or a reaction product of --N(H)--
with an epoxy functional group, a cycloalkylepoxy functional group,
a glycidyl ether functional group, an acid anhydride functional
group, or a lactone; each X is independently a divalent a
carboxylic acid, phosphate, sulfate, sulfonate or quaternary
ammonium radical, and with the proviso that each R.sup.3 and each
R.sup.4 may be the same or different; where the method comprises
the steps of: 1) reacting an organofunctional polyorganosiloxane
with a sugar moiety to produce the saccharide siloxane copolymer in
the presence of a solvent; optionally ii) removing a portion of the
solvent; and iii) adding an oil.
17. The method of claim 16, where each R.sup.5 and each R.sup.7 are
independently an alkyl group of 1 to 12 carbon atoms.
18. The method of claim 16, where the oil is added before and/or
during step i).
19. The method of claim 16, where the oil is added during and/or
after step ii).
20. The method of claim 16, further comprising 4) removing the
solvent.
21. The method of claim 16, where step i) is performed by reacting
ingredients comprising: (A) an amino-functional polyorganosiloxane,
and (B) a sugar lactone.
22. The method of claim 21, where ingredient (A) is ##STR00006##
where each R.sup.12 is independently a monovalent hydrocarbon
group; each R.sup.13 is independently a divalent organic group;
each R.sup.14 is independently a hydrogen atom or a monovalent
hydrocarbon group of 1 to 4 carbon atoms; each subscript x is
independently 0 or 1; subscript v has a value ranging from 0 to
10,000; and subscript w has a value ranging from 0 to 10,000.
23. The method of claim 22, where ingredient (A) is selected from
trimethylsiloxy-terminated
poly(dimethylsiloxane/methyl(aminoethylaminoisobutyl)siloxane),
trimethylsiloxy-terminated
poly(dimethylsiloxane/methyl(aminopropyl)siloxane),
trimethylsiloxy-terminated
poly(dimethylsiloxane/methyl(aminoethylaminopropyl)siloxane), and
combinations thereof.
24. The method of claim 21, where ingredient (B) is ##STR00007##
where each R.sup.11 is independently a hydrogen atom, a hydroxyl
group, an alkoxy group, or a saccharide group; and subscript u has
a value ranging from 5 to 12.
25. The method of claim 24 where ingredient (B) is selected from
butyrolactone, epsilon caprolactone and delta gluconolactone.
26. The method of claim 21, where step i) is performed by reacting
ingredients comprising: (A) an epoxy-functional polyorganosiloxane,
and (B) an n-alkyl glucamine.
27. The method of claim 26, where ingredient (A) is ##STR00008##
where each R.sup.12 is independently a monovalent hydrocarbon
group; each R.sup.15 is independently an epoxy functional organic
group; each subscript x is independently 0 or 1; subscript v has a
value ranging from 0 to 10,000; and subscript w has a value ranging
from 0 to 10,000.
28. The method of claim 26, where the n-alkyl glucamine is n-methyl
glucamine.
29. The method of claim 26, further comprising preparing the epoxy
functional polyorganosiloxane by hydrosilylation of ingredients
comprising an alkenyl functional epoxy containing compound and a
polyorganohydrogensiloxane.
30. The method of claim 29, where the alkenyl functional epoxy
containing compound is allyl glycidyl ether, dodecyl glycidyl
ether, tetradecyl glycidyl ether, or octadecylglycidyl ether.
31. The method of claim 26, where the ingredients further comprise
an alkene.
32. The method of claim 31, where the alkene comprises
undecene.
33. The method of claim 21, where step i) is performed by a method
comprising: 1) reacting (a) an n-alkyl-glucamine with (b) an
alkenyl functional epoxy compound, and 2) hydrosilylating the
product of step 1) with (c) a polyorganohydrogensiloxane.
34. The method of claim 33, where the n-alkyl glucamine is n-methyl
glucamine.
35. The method of claim 33, where the alkenyl functional epoxy
containing compound is allyl glycidyl ether, dodecyl glycidyl
ether, tetradecyl glycidyl ether, or octadecylglycidyl ether.
36. The method of claim 21, where the product of step i) contains
secondary amine functionality, further comprising a step of
reacting the product of step i) with a capping agent selected from
a lactone, a halogenated unsaturated compound, an epoxy functional
compound, or an acid anhydride.
37. The method of claim 16, where the solvent is an alcohol
selected from methanol, ethanol, n-propanol, isopropanol,
2-propanol, isobutanol, n-butanol, and combinations thereof.
38. The method of claim 16, where the oil is a silicone oil.
39. The method of claim 38, where the oil is a
polydialkylsiloxane.
40. The method of claim 16, where the oil is an organic oil
selected from a hydrocarbon oil, an ester, a vegetable oil, a
mineral oil, or a fatty alcohol.
41. The method of claim 16, where the copolymer and the oil are
present in an amounts such that a weight ratio of copolymer/oil
ranges from 1/1 to 1/50.
42. A method for preparing an emulsion comprising I) adding an
aqueous phase to the product prepared by the method of any one of
claims 16 to 41, and II) mixing.
43. The method of claim 42, where the method further comprises step
III) subjecting the emulsion to shear during and/or after step
II).
44. The method of claim 42, where step I) and step II) are
performed incrementally by adding a portion of the aqueous phase,
mixing, and thereafter repeating until all of the aqueous phase is
added.
45. The method of claim 42, where step I) and step II) are
performed by adding the aqueous phase continuously over a period of
time while mixing is performed.
46. The method of claim 42, further comprising adding a second oil
during step I).
47. The method of claim 42, where the aqueous phase is present in
an amount ranging from 20% to 95% by weight based on the weight of
the emulsion.
Description
CROSS-REFERENCE TO RELATED APPLICATIONS and STATEMENT REGARDING
FEDERALLY SPONSORED RESEARCH
[0001] None.
BACKGROUND OF THE INVENTION
[0002] Saccharide siloxanes are known in the art. Saccharide
siloxanes comprising a hydroxyl functional saccharide component and
an organosiloxane component were found to be useful when applied to
hair, skin, fabric, paper, wood and other substrates. The
saccharide component may be covalently bound to the organosiloxane
at one or more pendant or terminal positions, or some combination
thereof, through linkages including but not limited to ether,
ester, and amide bonds.
BRIEF SUMMARY OF THE INVENTION
[0003] A saccharide siloxane copolymer (copolymer) is useful as an
emulsifier. Emulsions containing the copolymer are useful for
personal care applications.
DETAILED DESCRIPTION OF THE INVENTION
[0004] A saccharide siloxane copolymer (copolymer) is useful as an
emulsifier, for water in oil (w/o) type emulsions, such as water in
silicone emulsions. The copolymer comprises a saccharide component
and a siloxane component. The siloxane component forms the backbone
of the copolymer molecule. Saccharide components may be bonded to
the siloxane backbone in terminal groups, pendant groups, or both
terminal and pendant groups. Alternatively, the saccharide
component may be bonded to the siloxane backbone in a pendant
group.
[0005] The copolymer may be a solid or a fluid under ambient
conditions of temperature and pressure, e.g., at 25.degree. C. and
760 mmHg. Whether the copolymer is a solid at ambient conditions,
or a fluid such as a liquid or a gum, depends on various factors
including the degree of polymerization (DP) of the copolymer. The
copolymer may have a DP ranging from 2 to 15,000, alternatively 5
to 10,000, alternatively 50 to 5,000, alternatively, 100 to 1,000,
alternatively 50 to 1,000, and alternatively 100 to 400.
[0006] Alternatively, the copolymer may be a fluid under ambient
conditions of temperature and pressure, e.g., at 25.degree. C. and
760 mmHg. The viscosity of the copolymer depends on various factors
including the degree of polymerization (DP) of the copolymer. The
copolymer may have a DP ranging from 2 to 500, alternatively 5 to
500, alternatively, 25 to 500, alternatively 50 to 400,
alternatively 100 to 400, and alternatively 50 to 350.
[0007] The copolymer has general formula:
R.sup.2.sub.aR.sup.1.sub.(3-a)SiO--[(SiR.sup.2R.sup.1O).sub.m--(SiR.sup.-
1.sub.2O).sub.n].sub.y--SiR.sup.1.sub.(3-a)R.sup.2.sub.a; where
[0008] each R.sup.1 can be the same or different and each R.sup.1
comprises hydrogen, an alkyl group of 1 to 12 carbon atoms, an
organic group, or a group of formula R.sup.3-Q; [0009] Q comprises
an epoxy, cycloalkylepoxy, primary or secondary amino,
ethylenediamine, carboxy, halogen, vinyl, allyl, anhydride, or
mercapto functionality; [0010] subscripts m and n are integers from
0 to 15,000 and may be the same or different; each subscript a is
independently 0, 1, 2, or 3; [0011] subscript y is an integer such
that the copolymer has a molecular weight less than 1 million;
[0012] each R.sup.2 has formula Z-(G.sup.1).sub.b-(G.sup.2).sub.c,
and there is an average of at least one R.sup.2 per copolymer
molecule, where [0013] G.sup.1 is a saccharide component comprising
5 to 12 carbon atoms, a quantity (b+c) has a value ranging from 1
to 10, and subscript b or subscript c can be 0, [0014] G.sup.2 is a
saccharide component comprising 5 to 12 carbon atoms additionally
substituted with organic or organosilicon radicals, [0015] each Z
is a linking group and is independently selected from the group
consisting of: --R.sup.3--N(R.sup.8)--C(O)--R.sup.4--,
--R.sup.3--CH(OH)--CH.sub.2--N(R.sup.8)--R.sup.4--, or
R.sup.3--CH(N(R.sup.4)(R.sup.8))CH.sub.2OH; [0016] where each
R.sup.3 and each R.sup.4 are divalent spacer groups comprising a
group of formula (R.sup.5).sub.r(R.sup.6).sub.s(R.sup.7).sub.t,
[0017] where at least one of subscripts r, s and t is 1, and each
R.sup.5 and each R.sup.7 are independently either an alkylene group
of 1 to 12 carbon atoms or a group of formula (R.sup.9O).sub.p,
where [0018] subscript p is an integer with a value ranging from 1
to 50, and [0019] each R.sup.9 is a divalent organic group, and
[0020] each R.sup.9O may be the same or different, [0021] each
R.sup.6 is --N(R.sup.8)--, where R.sup.8 is selected from R.sup.3,
a monovalent hydrocarbon group, a group of formula Z--X, or a
reaction product of --N(H)-- with an epoxy functional group, a
cycloalkylepoxy functional group, a glycidyl ether functional
group, an acidic anhydride functional group, or a lactone; [0022]
each X is independently a divalent carboxylic acid, phosphate,
sulfate, sulfonate or quaternary ammonium radical, and [0023] with
the provisos that [0024] at least one of R.sup.3 and R.sup.4 must
be present in the linking group, and [0025] each R.sup.3 and each
R.sup.4 may be the same or different.
[0026] Each R.sup.1 can be the same or different. Each R.sup.1
comprises hydrogen, an alkyl group of 1 to 12 carbon atoms, an
organic group, or a group of formula R.sup.3-Q. Group Q comprises
an epoxy, cycloalkylepoxy, primary or secondary amino,
ethylenediamine, carboxy, halogen, vinyl, allyl, anhydride, or
mercapto functionality.
[0027] Subscripts m and n are integers from 0 to 15,000 and may be
the same or different. Alternatively, each subscript m may be 0 to
500 and each subscript n may be 0 to 500. Each subscript a is
independently 0, 1, 2, or 3. Alternatively, each subscript a may be
0. When subscript a is 0, then at least one of subscripts m and n
is greater than 0, and all of the saccharide components are in
pendant groups (not terminal groups) on the copolymer. Subscript y
is an integer such that the copolymer has a molecular weight less
than 1 million. Subscript y, and at least one of subscripts m and
n, may be greater than 0 such that a saccharide component is in a
pendant group on the copolymer.
[0028] Each R.sup.2 has formula Z-(G.sup.1).sub.b-(G.sup.2).sub.c,
and there is an average of at least one R.sup.2 per 10 copolymer
molecule. Group G.sup.1 is a saccharide component comprising 5 to
12 carbon atoms. Subscript b or subscript c can be 0. However, a
quantity (b+c) has a value ranging from 1 to 10. Group G.sup.2 is a
saccharide component comprising 5 to 12 carbon atoms additionally
substituted with organic or organosilicon groups. Substituted means
that a hydrogen atom bonded to a carbon atom has been replaced with
another substituent, such as with an organic group or an
organosilicon group. Each Z is a linking group.
[0029] Each Z is independently selected from the group consisting
of: --R.sup.3--N(R.sup.8)--C(O)--R.sup.4--,
--R.sup.3--CH(OH)--CH.sub.2--N(R.sup.8)--R.sup.4--, or
--R.sup.3--CH(N(R.sup.4)(R.sup.8))CH.sub.2OH. Each R.sup.3 and each
R.sup.4 are divalent spacer groups comprising a group of formula
(R.sup.5).sub.r(R.sup.6).sub.s(R.sup.7).sub.t. At least one of
subscripts r, s and t is 1. Each R.sup.5 and each R.sup.7 are
independently either an alkylene group of 1 to 12 carbon atoms or a
group of formula (R.sup.9O).sub.p. Subscript p is an integer with a
value ranging from 1 to 50. Each R.sup.9 is a divalent organic
group. Each R.sup.9O may be the same or different. Alternatively,
each R.sup.5 and each R.sup.7 are independently an alkylene group
of 1 to 12 carbon atoms, and the copolymer may be free of groups of
formula R.sup.9O. Without wishing to be bound by theory, it is
thought that copolymers free of groups of formula R.sup.9O when
used as emulsifiers may provide low odor emulsions. Each R.sup.6 is
--N(R.sup.8)--, where R.sup.8 is selected from R.sup.3, a group of
formula Z--X, a monovalent hydrocarbon group, or a reaction product
of --N(H)-- with an epoxy functional group, a cycloalkylepoxy
functional group, a glycidyl ether functional group, an acetic
anhydride functional group, or a lactone. Suitable monovalent
hydrocarbon groups for R.sup.8 may be a saturated hydrocarbon group
or an unsaturated hydrocarbon group. When R.sup.8 is an unsaturated
hydrocarbon group, R.sup.8 may be an alkenyl group. The alkenyl
group may have 2 to 12 carbon atoms and is exemplified by vinyl,
allyl, decenyl, and dodecenyl. Alternatively, the alkenyl group may
have a longer chain such as at least 14 carbon atoms. When R.sup.8
is a saturated hydrocarbon group, R.sup.8 may be an alkyl group.
The alkyl group may be relatively short chain, such as 1 to 12
carbon atoms. Alternatively, the alkyl group may have a longer
chain, such as at least 14 carbon atoms. Each X is independently a
divalent a carboxylic acid, phosphate, sulfate, sulfonate or
quaternary ammonium radical. At least one of R.sup.3 and R.sup.4
must be present in the linking group. Each R.sup.3 and each R.sup.4
may be the same or different.
Method of Making the Copolymer
[0030] The copolymer described above may be made by a method
comprising: 1) reacting an organofunctional polyorganosiloxane with
a sugar moiety to produce a saccharide siloxane copolymer as
described above and 2) removing all or a portion of a solvent, if a
solvent is present.
[0031] In one embodiment, the method for making the copolymer
comprises:
1) reacting an amine functional polyorganosiloxane containing a
primary amine and a secondary amine with a sugar lactone to consume
the primary amine, 2) reacting the product of step 1) with a
capping agent to block the secondary amine.
[0032] Steps 1) and 2) may be performed sequentially.
Alternatively, step 1 and step 2 may be combined and performed
simultaneously.
[0033] The secondary amine functionality may be selected from
aminopropyl, aminoethylaminopropyl, and aminoethylaminoisobutyl.
The sugar lactone may be an aldonolactone or another lactone
derived from a saccharide. Aldonolactones are lactones derived from
aldonic acids. The capping agent may be a lactone, a halogenated
unsaturated compound, an epoxy functional compound, or an acid
anhydride.
[0034] Step 1) may be performed by reacting (A) an amino-functional
polyorganosiloxane and (B) an aldonolactone. Ingredient (A) may
have the formula:
##STR00001##
where each R.sup.10 is a independently secondary amino group; each
R.sup.11 is independently a monovalent hydrocarbon group or
R.sup.10; subscript w has a value ranging from 0 to 10,000, and
subscript v has a value ranging from 0 to 10,000, with the proviso
that when all instances of R.sup.11 are monovalent hydrocarbon
groups, then subscript w is greater than 0. The secondary amino
group may be, for example, aminoethylaminoisobutyl or
aminoethylaminopropyl.
[0035] Ingredient (A) is exemplified by trimethylsiloxy-terminated
poly(dimethylsiloxane/methyl(aminoethylaminoisobutyl)siloxane);
trimethylsiloxy-terminated
poly(dimethylsiloxane/methyl(aminoethylaminopropyl)siloxane);
dimethyl, methyl(aminoethylaminoisobutyl)siloxy-terminated,
polydimethylsiloxane; dimethyl,
methyl(aminoethylaminopropyl)siloxy-terminated,
polydimethylsiloxane; and combinations thereof.
[0036] Ingredient (B) is an aldonolactone or another lactone
derived from a saccharide. The aldonolactone suitable for
ingredient (B) is exemplified by gluconolactone (GL),
erythronolactone, galactonolactone, gluconolactone, mannonolactone,
and ribolactone. Other lactones derived from saccharides can
include glucoronolactone, glucoheptanolactone, glucooctanolactone,
isocitric acid lactone, saccharolactone, and lactobionolactone
(LBL). Alternatively, ingredient (B) may be GL or LBL. Lactones
suitable for ingredient (B) are commercially available.
[0037] Step 2) may be performed by reacting the product of step 1)
with (C) a capping agent to block the secondary amine. The capping
agent may be a lactone, a halogenated unsaturated compound capable
of reacting with the hydrogen on the secondary amine functionality,
an epoxy functional compound, or an acid anhydride.
[0038] The capping agent may be a lactone. The lactone may have the
formula:
##STR00002##
Each R.sup.12 is independently a hydrogen atom, a hydroxyl group,
an alkoxy group, or a saccharide group. Alkoxy groups are
exemplified by methoxy, ethoxy, propoxy, and butoxy. Alternatively,
each R.sup.12 is a hydroxyl group or a saccharide group. Subscript
u has a value ranging from 5 to 12. The lactone used in step 2) may
be exemplified by the sugar lactones described above.
Alternatively, the lactone may be butyrolactone, epsilon
caprolactone, gamma gluconolactone, delta gluconolactone, and LBL.
Alternatively, the lactone may be gamma gluconolactone or delta
gluconolactone.
[0039] Alternatively, the capping agent may be halogenated
unsaturated compound capable of reacting with the hydrogen atom on
the secondary amine. The halogenated unsaturated compound may be a
halogenated unsaturated hydrocarbon such as an alkenyl chloride.
Suitable alkenyl chlorides may have 2 to 12 carbon atoms and may
include vinyl chloride, allyl chloride, decyl chloride, or dodecyl
chloride.
[0040] Alternatively, the capping agent may be an epoxy functional
compound. The epoxy functional compound may be selected from allyl
epoxy functional compounds, cycloalkylepoxy functional compounds,
glycidyl ether functional compounds, and glycidol.
[0041] Alternatively, the capping agent may be an acidic anhydride.
The acid anhydride may have the formula:
##STR00003##
where each R.sup.13 is independently a monovalent hydrocarbon
group.
[0042] Alternatively, each R.sup.13 may be an alkyl group, such as
an alkyl group of 1 to 12 carbon atoms. Suitable alkyl groups are
represented by methyl, ethyl, propyl, and butyl. Alternatively, the
acid anhydride may comprise acetic anhydride, chloroacetic
anhydride, propionic anhydride, crotonic anhydride, methacrylic
anhydride, butyric anhydride, isobutyric anhydride, diethyl
pyrocarbonate, or 4-pentenoic anhydride. Alternatively, the acid
anhydride may be acetic anhydride.
[0043] Alternatively, the copolymer may be prepared by a method
comprising reacting an epoxy functional polyorganosiloxane with an
n-alkyl glucamine such as n-methyl glucamine. The epoxy functional
polyorganosiloxane may be prepared by methods known in the art,
such as by hydrosilylation of ingredients comprising an alkenyl
functional epoxy containing compound and a
polyorganohydrogensiloxane. The alkenyl functional epoxy containing
compound may be allyl glycidyl ether, dodecenyl glycidyl ether,
tetradecenyl glycidyl ether, or octadecenylglycidyl ether. The
ingredients may optionally further comprise further comprise an
alkene, such as undecene. Alternatively, one skilled in the art
could react the n-alkyl-glucamine first with the alkenyl functional
epoxy containing compound and thereafter perform the
hydrosilylation reaction to attach the product thereof to the
polyorganohydrogensiloxane.
[0044] Alternatively, the copolymer may be prepared by a method
comprising:
1) reacting an n-alkyl-glucamine with an alkenyl functional epoxy
compound, and 2) hydrosilylating the product of step 1) with a
polyorganohydrogensiloxane.
[0045] Steps 1) and 2) may be performed sequentially.
Alternatively, step 1 and step 2 may be combined and performed
simultaneously.
[0046] In this method, the alkenyl functional epoxy containing
compound may be allyl glycidyl ether, dodecyl glycidyl ether,
tetradecyl glycidyl ether, or octadecylglycidyl ether. The n-alkyl
glucamine may be n-methyl glucamine.
[0047] The methods described above may be performed neat or in the
presence of a solvent. The solvent may be an alcohol such as
methanol, ethanol, propanol, butanol, or a combination thereof.
Alternatively, the organo-functional polyorganosiloxane (e.g.,
amine functional polyorganosiloxane, or epoxy functional
polyorganosiloxane, or the polyorganohydrogensiloxane) may be
dissolved in a solvent such as ethanol with the other ingredients
used in the method. All or a portion of the solvent may be removed,
for example, by stripping or distillation, after the method is
complete. Alternatively, the copolymer may be left in the solvent
after the method is complete, for example, if the solvent is a
suitable ingredient for an emulsion in which the copolymer will be
formulated.
[0048] Alternatively, the methods described above may be performed
in the presence of an oil. The oil may be added in addition to the
solvent. The oil may be added before reacting the ingredients to
make the copolymer. Alternatively, the oil may be added during
and/or after making the copolymer and before removal of any
solvent. Alternatively, the oil may be added after a portion of the
solvent is removed. Alternatively, the oil may be added after all
of the solvent is removed.
[0049] The methods described above may be performed by heating. The
exact temperature depends on various factors including the specific
ingredients selected, however, temperature may range from
50.degree. C. to 100.degree. C. and reaction time for each step may
be several hours, alternatively, up to 10 hours, alternatively 1 to
10 hours. The first and second steps in the methods described above
may be performed sequentially. Alternatively, step 1 and step 2 may
be combined and performed simultaneously.
[0050] In the methods described above a molar excess may be used of
the functionality on the reagent reacting with the functionality on
the polyorganosiloxane. For example, in the hydrosilylation of
allyl glycidyl ether with an SiH intermediate polyorganosiloxane, a
1.1:1 ratio is used of the moles allyl glycidyl ether to the moles
of SiH. The ratio for the reagent to siloxane bonded functionality
may be as large as 1.8:1. Alternatively, the molar ratio may range
from 1:1 to 1.8:1, alternatively 1.1:1 to 1.5:1.
[0051] Alternatively, the molar ratio of sugar lactone to amine may
be 1:1, calculated from amine value of the amine functional
polyorganosiloxanes. However, the molar ratio of sugar
functionality in the sugar lactone to amine in the amine functional
polyorganosiloxane may range from 0.5:1 to 2.0:1.
Definitions and Usage of Terms
[0052] All amounts, ratios, and percentages are by weight unless
otherwise indicated. As used herein, the articles `a` `an` and
`the` each refer to one or more, unless otherwise indicated by the
context of the application.
[0053] The art of "personal care" is intended to include any
topical treatment of any portion of the body that is intended to
provide a benefit to that portion of the body. The a benefit may be
direct or indirect, and may be sensory, mechanical, cosmetic,
protective, preventative or therapeutic. While it is contemplated
that the human body is a particularly desirable target substrate
for the presently disclosed personal care compositions and products
formulated therefrom, it will be readily apparent to one skilled in
the art that other mammals having similar tissues, especially
keratinacious tissue such as skin and hair, may be suitable target
substrates and that therefore veterinary applications are within
the scope of the present invention.
[0054] The personal care compositions, as provided, are adapted to
provide a benefit to a portion of the body. As used herein,
"adapted" means formulated in a manner that permits safe and
effective application of the benefit to the portion of the body. As
used herein, "safe and effective" means an amount that provides a
level of benefit perceivable by a consumer seeking such a benefit
without damaging or causing significant discomfort to the consumer
seeking such a benefit. A significant discomfort is one that
outweighs the benefit provided such that an ordinary consumer will
not tolerate it.
[0055] A person of ordinary skill in the personal care formulation
arts will appreciate the well-known criterion for selecting the
essential ingredients, optional additives and excipients, that are
suitable according to the intended application of a particular
personal care composition. Non-limiting examples of additives which
may be formulated into the personal care compositions with the
emulsion include: additional silicones, aerosols, anti-oxidants,
cleansing agents, colorants, additional conditioning agents,
deposition agents, electrolytes, emollients and oils, exfoliating
agents, foam boosters, fragrances, humectants, occlusive agents,
pediculicides, pH control agents, pigments, preservatives,
biocides, other solvents, stabilizers, sunscreening agents,
suspending agents, tanning agents, other surfactants, thickeners,
vitamins, botanicals, waxes, rheology-modifying agents,
anti-dandruff, anti-acne, anti-carie and wound healing-promotion
agents.
[0056] The term "emulsion" as used herein means a two phase system
comprising two immiscible liquids with the liquid constituting the
first, dispersed internal (discontinuous) phase being suspended in
the second, continuous phase with the aid of the copolymer
described above as an emulsifier.
Emulsions
[0057] The copolymer described above was surprisingly found to have
improved emulsification properties as compared to some previously
known saccharide siloxanes. Therefore, an emulsion including the
copolymer as an emulsifier may be prepared. The emulsion may be a
water in oil (w/o) emulsion comprising an internal, aqueous phase
comprising water and an external, continuous phase comprising an
oil and the copolymer as the emulsifier. Without wishing to be
bound by theory, it is thought that the emulsion need not further
comprise any surfactant other than the copolymer to maintain the
dispersion of the internal phase.
[0058] The oil used in the continuous phase of the emulsion may be
a silicone oil or an organic oil. The oil may be a silicone oil
such as a polydialkylsiloxane having a viscosity of 1 to 350 cSt.
Such silicone oils are commercially available as DOW CORNING.RTM.
200 Fluids with viscosities ranging from 2 centiStokes (cSt) to 350
cSt, and DOW CORNING.RTM. FZ-3196, DOW CORNING.RTM. 244 Fluid, and
DOW CORNING.RTM. 245 Fluid from Dow Corning Corporation of Midland,
Mich., U.S.A. Dimethicone oils from Dow Corning Corporation include
244 Fluid, 245 Fluid, and 200 Fluids with viscosity of 2 cSt, 5
cSt, 10 cSt 20 cSt, 50 cSt, 100 cSt, or 350 cSt.
[0059] Alternatively, certain organic oils are suitable for use in
the emulsion. Suitable organic oils include esters, vegetable
and/or mineral oils, hydrocarbon oils, or fatty alcohols.
[0060] Suitable esters include isopropyl myristate, octyl
octanonanoate, decyl oleate, isopropyl palmitate, glyceryl
stearate, ethylhexyl stearate, isopropyl isostearate, C12-C15 alkyl
benzoate, octyl cocoate, octyl palmitate, myristyl lactate, and
dioctyl adipate. Examples of esters further comprise cetyl
ethylhexanoate (which is commercially available as Schercemol.TM.
Colo. Ester from The Lubrizol Corporation of Wickliffe, Ohio,
U.S.A.) and triethylhexanoin (which is commercially available as
Schercemol.TM. GTO Ester, also from Lubrizol).
[0061] Suitable vegetable and mineral oils include almond oil,
apricot kernel, avocado oil, castor oil, evening primrose, jojoba
oil, sunflower oil, olive oil, wheat germ oil, and mineral oil.
[0062] Suitable hyrocarbon oils include petrolatum, mineral oil,
squalene, capric/caprylic triglyceride; an alkane of at least 12
carbon atoms. For example, long chain alkanes (e.g., alkanes having
at least 12 carbon atoms, such as isododecane or isohexadecane) may
be used as the organic oil.
[0063] Suitable fatty alcohols that include strearyl alcohol, cetyl
alcohol.
[0064] The emulsion may be prepared by a method comprising
dispersing the copolymer described above in an oil and thereafter
adding the aqueous phase. The aqueous phase may be added to the oil
phase in increments with mixing between additions. The resulting
combination of aqueous and oil phases may be subjected to high
shear. The oil forms the external or continuous phase. Mixing may
be performed, for example, by mixing with a cross stirrer at 700 to
1,000 revolutions per minute (rpm) while adding the aqueous phase.
After the aqueous phase has been added, the resulting mixture may
optionally be further mixed at 1,000 to 2,000 rpm for a period of
time such as 1 second to 10 minutes, alternatively 1 minute to 5
minutes. For example, mixing conditions after all the aqueous phase
have been added may include mixing for 1 minute at 1,000 rpm and
then 5 minutes at 2,000 rpm. A low shear mixer, such as a planetary
type mixer may be used for this method step. Without wishing to be
bound by theory, it is thought that the emulsion may be a coarse
emulsion that may have a relatively large particle size (e.g., on
the order of 5 micrometers or higher) using low shear mixing.
[0065] The high shear mixing may be performed using special
equipment, which allows to the emulsion mix at very high shear to
reduce particle size and increase the viscosity of the emulsion.
High shear mixing may improve stability of the emulsion. The high
shear mixing may be performed with a commercially available high
shear device, e.g., a homogenizer such as a T25 Digital
ULTRA-TURRAX.RTM. commercially available from IKA of Wilmington,
N.C., U.S.A. or a homogenizer such as L4RT commercially available
from Silverson Machines Ltd. of England. The exact conditions for
high shear mixing will vary depending on factors such as the
initial viscosity of the emulsion, however, high shear conditions
are exemplified by mixing the emulsion at 7,000 to 8,000 rpm for 1
second to 1 minute, alternatively 15 seconds. Without wishing to be
bound by theory, it is thought that the emulsion may be a fine
emulsion that may have a relatively small particle size (e.g., on
the order of less than 5 micrometers) after high shear mixing.
[0066] It will be understood by one of ordinary skill in the art
that there is a continuum for the ease with which a desired
emulsion forms. The emulsions described herein share similar
constraints with other emulsions. That is, they are
thermodynamically unstable and need an input of energy to initiate
emulsification. Simple agitation via mixing may be sufficient, or
higher shear means including the employment of high shear devices
may be used. Alternatively, an inversion method may be used.
[0067] A degree of agitation necessary to form the emulsion may
require employment of mixing devices. Mixing devices typically
provide the required energy input. Non-limiting examples of these
mixing devices spanning the shear range include: 1) a vessel with
an impeller, for example, propeller, pitched blade impeller,
straight blade impeller, Rushton impeller, or Cowles blade; 2)
kneading type mixers, for example, Baker-Perkins; 3) high shear
devices which use positive displacement through an orifice to
generate shear, for example, homogenizer, sonolator, or
microfluidizer; 4) high shear devices using a rotor and stator
configuration, for example, colloid mills, homomic line mills,
homogenizers from IKA, or Bematek; 5) continuous compounders with
single or dual screws; 6) change can mixers with internal impellers
or rotor/stator devices, for example, Turello mixer; and 7)
centrifugal mixers, for example, Hauschild speedmixers.
Combinations of mixing devices can also provide benefits, for
example a vessel with an impeller can be connected to a high shear
device. High shear devices are known in the art and are
commercially available, for example, the high shear device may be a
homogenizer such as a T25 Digital ULTRA-TURRAX.RTM. commercially
available from IKA of Wilmington, N.C., U.S.A. or high shear mixer
from Silverson Machines Ltd. of England.
[0068] The choice of mixing device is based on the type of internal
phase to be emulsified. For example, low viscosity internal phases
can be emulsified using high shear devices which use positive
displacement through an orifice. However, in the case of high
viscosity internal phases, a rotor/stator device, twin screw
compounder or change can mixer are often better choices.
[0069] The order of ingredient addition in the preparation of the
emulsion may be determined empirically. For example, a desirable
order of addition for a thick-phase emulsification may be: (a)
combine the copolymer with an oil; (b) add aqueous phase comprising
water in increments with shear until a thick phase emulsion forms;
and optionally (c) further dilute with additional oil and/or oil
phase to a desired concentration, with shear. The method may
optionally further comprise adding an additional ingredient, such
as those described below.
[0070] Emulsions made with the copolymer may be useful in personal
care products. Therefore, the method may optionally further
comprise formulating a personal care product with the emulsion. The
personal care products may be functional with respect to the
portion of the body to which they are applied, cosmetic,
therapeutic, or some combination thereof. Conventional examples of
such products include, but are not limited to: antiperspirants and
deodorants, skin creams, skin care lotions, moisturizers, facial
treatments such as acne or wrinkle removers, personal and facial
cleansers, bath oils, perfumes, colognes, sachets, sunscreens,
pre-shave and after-shave lotions, shaving soaps, and shaving
lathers, hair shampoos, hair conditioners, hair colorants, hair
relaxants, hair sprays, mousses, gels, permanents, depilatories,
and cuticle coats, make-ups, color cosmetics, foundations,
concealers, blushes, lipsticks, eyeliners, mascara, oil removers,
color cosmetic removers, wrinkle fillers, skin imperfection hiders,
skin surface smoothers, eyelash curlers, nail varnishes, hair
make-up products, eye shadows, body makeups, and powders,
medicament creams, pastes or sprays including anti-acne, dental
hygienic, antibiotic, healing promotive, nutritive and the like,
which may be preventative and/or therapeutic. In general the
personal care products may be formulated with a carrier that
permits application in any conventional form, including but not
limited to liquids, rinses, lotions, creams, pastes, gels, foams,
mousses, ointments, sprays, aerosols, soaps, sticks, soft solids,
solid gels, and gels. What constitutes a suitable carrier is
readily apparent to one of ordinary skill in the art.
[0071] In some personal care product embodiments comprising the
emulsion, inclusion of the copolymer may decrease the need for
other thickening agents in the formulation. In these embodiments,
desired viscosity or thickness of the product is maintained with a
lesser amount than is typical of conventional thickeners. This is
particularly desirable in products wherein the thickening agent
antagonizes a desirable effect of another benefit agent, such as,
for example, a conditioning agent. It is also desirable in products
where one or more thickening agents are included for processing or
formulation characteristics rather than for any desired benefit
they provide to the portion of the body to which they are applied.
In these cases, the copolymer may permit a decrease in the one or
more thickening agents that possess antagonistic performance
characteristics.
[0072] In a specific embodiment of the personal care product
comprising the emulsion, the benefit comprises a conditioning
benefit and the portion of the body comprises hair. Specific
examples of the conditioning benefit include, but are not limited
to an anti-static, lubricity, shine, viscosity, tactile,
manageability, or a styling benefit. Non-limiting examples of
manageability benefits include ease of dry and/or wet combing.
Non-limiting examples of styling benefits include curl retention or
hair-relaxing benefits. The conditioner may be a rinse-off or
leave-in conditioner. In a specific embodiment the conditioning
benefit comprises a curl-retention benefit.
[0073] Examples of suitable conditioning agents include, but are
not limited to, cationic polymers, cationic surfactants, proteins,
natural oils, silicones other than the copolymer, hydrocarbons,
nonionic surfactants, amphoteric surfactants, or mixtures thereof.
Examples of additional silicones which may be useful in the present
personal care products include, but are not limited to: alkyl
methyl siloxanes, cyclic siloxanes, gums, linear siloxanes, MQ
siloxane resins, MTQ siloxane resins, and polyether siloxane
copolymers.
[0074] Further embodiments of the present invention are direct to
methods for providing a benefit to a portion of the body. One such
method comprises administration of a safe and effective amount of a
personal care product comprising the emulsion to a portion of the
body. In one specific embodiment, a method of treating hair
comprising administering a safe and effective amount of the
emulsion is provided. A very specific embodiment provides a method
of styling and holding hair comprising administering a safe and
effective amount of the emulsion.
[0075] Formulating personal care products with the emulsion as
described above may provide a thickening benefit. In a specific
embodiment, an antiperspirant, hair, skin and color cosmetic
products are provided. The antiperspirant product is formulated
with the personal care composition comprising the emulsion as
described above, wherein the benefit comprises a thickening benefit
sufficient to maintain suspension of antiperspirant salts when the
formulation comprises a substantially less than typical amount of
conventional thickeners. In specific embodiments, the
antiperspirant product is provided in the form of a solid, a soft
solid or a gel. In a more specific embodiment the solid form
comprises a soft solid or a gel.
[0076] Another specific embodiment provides a personal care product
comprising the novel personal care composition where the benefit
comprises an enhanced conditioning benefit and the portion of the
body comprises skin. An embodiment directed to a method of treating
skin is provided which comprises: (1) administration of a safe and
effective amount of the personal care product comprising the
emulsion; and (2) rubbing the safe and effective amount into the
skin.
[0077] Another specific embodiment is directed to a color cosmetic
product comprising the emulsion where the benefit comprises a
cosmetic benefit. More specific embodiments are directed to liquid
foundations.
[0078] In a specific embodiment, water in oil emulsion samples were
prepared according to the following general procedure. The oil
phase was prepared by mixing an emulsifier with an oil. The oil was
isopropyl myristate or DOW CORNING.RTM. 200 Fluid, a silicone oil
with a viscosity of 5 cSt, which is commercially available from Dow
Corning Corporation. The emulsifier was a copolymer as described
above. In each oil phase, the oil phase contained 10% emulsifier
and 90% oil. The aqueous phase was prepared by mixing water and
sodium chloride in a water: NaCl weight ratio of 99:1.
Alternatively, the aqueous phase may comprise water, sodium
chloride, and glycerol in a weight ratio (water: NaCl: glycerol) of
92.5:1.25:6.25. For each sample, the aqueous phase was added to the
oil phase in increments. Between the addition of each increment,
the sample was mixed for a period of time at 3400 revolutions per
minute (rpm) in a DAC150 FlackTek.TM. SpeedMixer.TM. (commercially
available from FlackTek, Inc. of Landrum, S.C., U.S.A.) to provide
a coarse emulsion.
[0079] After all the aqueous phase was added, the resulting coarse
emulsion was subjected to shear at .gtoreq.7,000 rpm in a
homogenizer (T25 Digital ULTRA-TURRAX.RTM. commercially available
from IKA of Wilmington, N.C., U.S.A.) to provide a fine
emulsion
[0080] The aqueous phase may be present in an amount ranging from
20% to 95%, alternatively 40 to 90%, and alternatively 60% to 80%
by weight based on the weight of the emulsion.
Personal Care Applications
[0081] The emulsion described above is useful in personal care
applications. When the emulsion described above is used in personal
care applications, the emulsion may further comprise an additional
ingredient, such as those described above. The additional
ingredient may be selected from additional silicones, aerosols,
anti-oxidants, cleansing agents, colorants, additional conditioning
agents, deposition agents, electrolytes, emollients and oils,
exfoliating agents, foam boosters, fragrances, humectants,
occlusive agents, pediculicides, pH control agents, pigments,
preservatives, biocides, other solvents, stabilizers, sunscreening
agents, suspending agents, tanning agents, other surfactants,
thickeners, vitamins, botanicals, waxes, rheology-modifying agents,
antiperspirants, anti-dandruff, anti-acne, anti-carie and wound
healing-promotion agents, an additional oil, a hydrophilic medium,
a filler, a fiber, a film forming polymer, an additional surfactant
and/or emulsifier, a dyestuff, a structuring agent, an active
ingredient, a fragrance, a preservative, and combinations thereof.
Alternatively, the additional ingredient can be selected from an
additional oil, a hydrophilic medium, a filler, a fiber, a film
forming polymer, an additional surfactant and/or emulsifier, a
dyestuff, a structuring agent, an active ingredient (such as a
personal care active), a fragrance, a preservative, or a
combination thereof.
Additional Oil
[0082] The additional oil may be another oil selected from the oils
as described above, or the oil may be chosen from hydrocarbon-based
oils, silicone oils and fluorinated oils. The oil may be chosen
from volatile oils and non volatile oils, and mixtures thereof.
[0083] For purposes of this application, the term
"hydrocarbon-based oil" means an oil formed essentially from, or
even consisting of, carbon and hydrogen atoms, and possibly oxygen
and nitrogen atoms, and containing no silicon or fluorine atoms; it
may contain ester, ether, amine, or amide groups.
[0084] For purposes of this application, the term "silicone oil"
means an oil containing at least one silicon atom, and
alternatively containing Si--O-- groups.
[0085] For purposes of this application, the term "fluorinated oil"
means an oil containing at least one fluorine atom.
[0086] For purposes of this application, the term "volatile oil"
means an oil (or non-aqueous medium) capable of evaporating on
contact with the skin in less than one hour, at room temperature
and atmospheric pressure. The volatile oil may be a volatile
cosmetic oil, which is liquid at room temperature, especially
having a non-zero vapor pressure, at room temperature and
atmospheric pressure, in particular having a vapor pressure ranging
from 0.13 Pa to 40 000 Pa (10.about.3 to 300 mmHg), alternatively
ranging from 1.3 Pa to 13 000 Pa (0.01 to 100 mmHg) and
alternatively ranging from 1.3 Pa to 1300 Pa (0.01 to 10 mmHg).
[0087] In addition, the volatile oil generally has a boiling point,
measured at atmospheric pressure, ranging from 150.degree. C. to
260.degree. C. and alternatively ranging from 170.degree. C. to
250.degree. C.
[0088] The emulsion may comprise a volatile hydrocarbon-based oil
chosen especially from hydrocarbon-based oils with a flash point
ranging from 40.degree. C. to 102.degree. C., alternatively ranging
from 40.degree. C. to 55.degree. C. and alternatively ranging from
40.degree. C. to 50.degree. C.
[0089] The volatile oil may be present in the emulsion in an amount
ranging from 0.1% to 80% by weight, alternatively ranging from 1%
to 70% by weight, and alternatively ranging from 5% to 50% by
weight, relative to the total weight of the emulsion.
[0090] The emulsion may comprise at least one non-volatile oil in a
non-volatile liquid fatty phase. The non-volatile oil may be
present in an amount ranging from 0.1% to 80% by weight,
alternatively ranging from 0.5% to 60% by weight, and alternatively
ranging from 1% to 50% by weight relative to the total weight of
the non-volatile liquid fatty phase.
[0091] The volatile hydrocarbon-based oils may be selected from
hydrocarbon-based oils containing from 8 to 16 carbon atoms, and
especially branched C8-C16 alkanes, for instance C8-C16 isoalkanes
of petroleum origin (also known as isoparaffins), for instance
isododecane (also known as 2,2,4,4,6-pentamethylheptane), isodecane
and isohexadecane, for example the oils sold under the trade names
Isopar or Permethyl, branched C8-C16 esters and isohexyl
neopentanoate, and combinations thereof.
[0092] Volatile oils that may also be used include volatile
silicones, for instance volatile linear or cyclic silicone oils,
especially those with a viscosity .ltoreq.8 centistokes
(8.times.10.sup.6 m.sup.2/s) and especially containing from 2 to 7
silicon atoms, these silicones optionally comprising alkyl or
alkoxy groups containing from 1 to 10 carbon atoms.
[0093] Volatile fluorinated solvents such as
nonafluoro-methoxybutane or perfluoromethylcyclopentane are also
suitable for use in the composition.
[0094] Non-volatile hydrocarbon-based oils include, but are not
limited to, hydrocarbon-based oils of plant origin, such as
triesters of fatty acids and of glycerol, the fatty acids of which
may have varied chain lengths from 4 to 24 carbon atoms, these
chains possibly being linear or branched, and saturated or
unsaturated. These oils are exemplified by wheat germ oil,
sunflower oil, grapeseed oil, sesame seed oil, corn oil, apricot
oil, castor oil, shea oil, avocado oil, olive oil, soybean oil,
sweet almond oil, palm oil, rapeseed oil, cottonseed oil, hazelnut
oil, macadamia oil, jojoba oil, alfalfa oil, poppyseed oil, pumpkin
oil, marrow oil, blackcurrant oil, evening primrose oil, millet
oil, barley oil, quinoa oil, rye oil, safflower oil, candlenut oil,
passionflower oil or musk rose oil; or caprylic and/or capric acid
triglycerides; synthetic ethers containing from 10 to 40 carbon
atoms; apolar hydrocarbon-based oils, for instance squalene, linear
or branched hydrocarbons such as liquid paraffin, liquid petroleum
jelly and naphthalene oil, hydrogenated or partially hydrogenated
polyisobutene, isoeicosane, squalane, decene/butene copolymers and
polybutene/polyisobutene copolymers, and polydecenes, and mixtures
thereof; synthetic esters, for instance oils of formula R'COOR'' in
which R' represents a linear or branched fatty acid residue
containing from 1 to 40 carbon atoms and R'' represents a
hydrocarbon-based chain, which is especially branched, containing
from 1 to 40 carbon atoms, on condition that R'+R''>10, for
instance cetostearyl octanoate, isopropyl myristate, isopropyl
palmitate, alkyl benzoates of 12 to 15 carbon atoms, hexyl laurate,
diisopropyl adipate, isononyl isononanoate, 2-ethylhexyl palmitate,
isostearyl isostearate, alcohol or polyalcohol octanoates,
decanoates or ricinoleates, for instance propylene glycol
dioctanoate; hydroxylated esters, for instance isostearyl lactate
or diisostearyl malate; and pentaerythritol esters; fatty alcohols
that are liquid at room temperature with a branched and/or
unsaturated carbon-based chain containing from 12 to 26 carbon
atoms, for instance octyldodecanol, isostearyl alcohol, oleyl
alcohol, 2-hexyldecanol, 2-butyloctanol or 2-undecylpenta-decanol;
higher fatty acids such as oleic acid, linoleic acid or linolenic
acid; carbonates; acetates; citrates; and combinations thereof.
[0095] The non-volatile silicone oils may be: non-volatile
polydimethylsiloxanes (PDMS); polydimethylsiloxanes comprising
alkyl or alkoxy groups, which are pendent and/or at the end of a
silicone chain, these groups each containing from 3 to 40 carbon
atoms; phenylsilicones; optionally fluorinated
polyalkylmethylsiloxanes; polysiloxanes modified with fatty acids,
fatty alcohols or polyoxyalkylenes, and combinations thereof.
Alkylmethylsiloxanes, which generally will have the formula
Me.sub.3SiO[Me.sub.2SiO].sub.A[MeR'''SiO].sub.BSiMe.sub.3, in which
R''' is a hydrocarbon group containing 6 to 30 carbon atoms, Me
represents methyl, and the degree of polymerization (DP), i.e., the
sum of A and B ranges from 3 to 50. Both the volatile and liquid
species of alkymethysiloxanes can be used in the composition.
[0096] The oil may alternatively comprise a silicone carbinol.
These materials are described in WO 03/101412 A2, and can be
commonly described as substituted hydrocarbyl functional siloxane
fluids or resins.
[0097] The emulsion may contain an oil with a molar mass ranging
from 650 to 10,000 g/mol, which may be selected from: lipophilic
polymers such as polybutylenes; polyisobutylenes, for example
hydrogenated polyisobutylenes; polydecenes and hydrogenated
polydecenes; vinylpyrrolidone copolymers such as a
vinylpyrrolidone/1-hexadecene copolymer (MM=7300 g/mol); esters
such as linear fatty acid esters with a total carbon number ranging
from 35 to 70, for instance pentaerythrityl tetrapelargonate;
hydroxylated esters such as polyglyceryl-2 triisostearate; aromatic
esters such as tridecyl trimellitate; and pentaerythritol esters,
and triisoarachidyl citrate, pentaerythrityl tetraisononanoate,
glyceryl triisostearate, glyceryl tris (2-decyl)tetradecanoate,
pentaerythrityl tetraisostearate, polyglyceryl-2 tetraisostearate,
and combinations thereof.
[0098] The emulsion may comprise a fluid silicone compound such as
a silicone gum or a silicone oil of high viscosity.
[0099] A polydimethylsiloxane with a viscosity at 25.degree. C.
ranging from 10 to 10,000,000 cSt., alternatively 1,000 to
2,500,000 cSt., alternatively 5,000 to 1,000,000 cSt., and
alternatively 10,000 to 60,000 cSt. may be selected.
[0100] The weight-average molecular mass of the fluid silicone may
range from 1,000 to 1, 500,000 g/mol, alternatively 200,000 to
1,000,000 g/mol.
[0101] The oil phase of the emulsion can also contain silicone
elastomer gels, elastomeric solid organopolysiloxane enclosed in a
fatty phase, where at least one elastomeric solid
organopolysiloxane is at least partially crosslinked. Examples of
such elastomeric solid organopolysiloxane are described in the
following Patents and Patent Publications U.S. Pat. No. 5,654,362,
EP 848029, EP 869142, WO2007109240, WO2007109260, WO2007109282,
WO2009006091, WO2010080755, U.S. Pat. No. 4,987,169, and U.S. Pat.
No. 5,760,116. These elastomer gels can be non emulsifying or self
emulsifying or a combination of both.
Hydrophilic Medium
[0102] The aqueous phase of the emulsion may comprise a hydrophilic
medium comprising water or a mixture of water and a hydrophilic
organic solvent, for instance alcohols, such as linear or branched
lower monoalcohols containing from 2 to 5 carbon atoms, for
instance ethanol, isopropanol or n-propanol, and polyols, for
instance glycerol, diglycerol, propylene glycol, sorbitol,
pentylene glycol and polyethylene glycols, or alternatively
hydrophilic C2 ethers and C.sub.2-C.sub.4 aldehydes.
[0103] The water or the mixture of water and of hydrophilic organic
solvents may be present in the emulsion in an amount ranging from
0.1% to 95% by weight and alternatively ranging from 10% to 80% by
weight relative to the total weight of the emulsion.
Fillers
[0104] The filler suitable for use in the emulsion described herein
may be mineral or organic, of any form, platelet-shaped, spherical
or oblong, irrespective of the crystallographic form (for example
lamellar, cubic, hexagonal, orthorhombic, etc.). Examples include
talc, mica, silica, kaolin, polyamide, poly-.beta.-alanine powder
and polyethylene powder, tetrafluoroethylene polymer powders,
lauroyllysine, starch, boron nitride, hollow polymer microspheres,
acrylic acid copolymers, silicone resin microbeads, elastomeric
polyorganosiloxane particles, precipitated calcium carbonate,
magnesium carbonate, magnesium hydrogen carbonate, hydroxyapatite,
hollow silica microspheres, glass or ceramic microcapsules, and
metal soaps for example zinc stearate, magnesium stearate, lithium
stearate, zinc laurate or magnesium myristate, polymethyl
methacrylate powders. Alternatively, the filler may be a
polyurethane powder.
[0105] Alternatively, the filler may be an elastomeric
organopolysiloxane powder. Advantageously, the elastomeric
organopolysiloxane is non-emulsifying. Spherical elastomeric
organopolysiloxanes are described in patent applications
JP-A-61-194 009, EP-A-242 219, EP-A-295 886 and EP-A-765 656. The
organopolysiloxane powders can also mixed with other particles as
described in patent publication U.S. Pat. No. 7,399,803.
[0106] The elastomeric organopolysiloxane powder may comprise at
least one elastomeric organopolysiloxane powder coated with
silicone resin, such as with silsesquioxane resin, as described,
for example, in patent U.S. Pat. No. 5,538,793.
[0107] Other elastomeric organopolysiloxanes in the form of
spherical powders may be hybrid silicone powders functionalized
with fluoroalkyl groups or hybrid silicone powders functionalized
with phenyl groups.
[0108] The filler may be an N-acylamino acid powder. The
N-acylamino acids may comprise an acyl group containing from 8 to
22 carbon atoms, for instance a 2-ethylhexanoyl, caproyl, lauroyl,
myristoyl, palmitoyl, stearoyl or cocoyl group. The amino acid may
be, for example, lysine, glutamic acid or alanine.
[0109] When present, the filler may be added to the emulsion in an
amount ranging from 0.01% to 30% by weight.
Fibers
[0110] For purposes of this application, the term "fiber" means an
object of length L and diameter D such that L is very much greater
than D, D being the diameter of the circle in which the cross
section of the fiber is inscribed.
[0111] In particular, the ratio L/D (or shape factor) ranges from
3.5 to 2500, alternatively 5 to 500, and alternatively 5 to
150.
[0112] The fiber that may be used in the emulsion may be fibers of
synthetic or natural, mineral or organic origin. The fiber that may
be used in the emulsion may be selected from polyamide, cellulose,
poly-p-phenylene-terephthamide or polyethylene fibers. Polyethylene
fibers may also be used.
[0113] The fibers may be present in the emulsion in an amount
ranging from 0.01% to 10% by weight.
Film-Forming Polymer
[0114] Certain film-forming polymers may be gelling agents. For the
purposes of this application, the term "film-forming polymer" means
a compound containing at least two repeating units and
alternatively at least three repeating units, where said compound
is capable, by itself or in the presence of an auxiliary
film-forming agent, of forming a macroscopically continuous film on
a support, especially on keratin materials, alternatively a
cohesive film and alternatively a film with cohesion and mechanical
properties such that said film can be isolated from said
support.
[0115] In one embodiment, the film-forming polymer is a film
forming organic polymer chosen from the group comprising:
film-forming polymers that are soluble in an organic liquid medium,
in particular liposoluble polymers, when the organic liquid medium
comprises at least one oil; film-forming polymers that are
dispersible in an organic solvent medium, in particular polymers in
the form of non-aqueous dispersions of polymer particles,
preferably dispersions in silicone oils or hydrocarbon-based
oils.
[0116] Alternatively, the film-forming polymers that may be used in
the emulsion may include synthetic polymers, of free-radical type
or of polycondensate type, polymers of natural origin, and mixtures
thereof. Such film-forming polymers include acrylic polymers,
polyurethanes, polyesters, polyamides, polyureas, cellulose-based
polymers, for instance nitrocellulose, silicone polymers, in
particular silicone resins, silicone-grafted acrylic polymers,
polyamide polymers and copolymers, and polyisoprenes.
[0117] The composition according to the invention may comprise, as
film-forming polymer, a dispersion of particles of a grafted
ethylenic polymer in the fatty phase.
[0118] Silicone-based macromonomers that may be used as the film
forming polymer include polydimethylsiloxanes containing
mono(meth)acrylate end groups. Silicone-based macromonomers that
may be used include monomethacryloxypropyl
polydimethylsiloxanes.
[0119] Alternatively, the emulsion may contain, as film-forming
polymer, a linear block ethylenic polymer, referred to hereinbelow
as a "block polymer". For purposes of this application, the term
"block polymer" means a polymer comprising at least two different
blocks and preferably at least three different blocks.
[0120] The polymer may be a polymer of linear structure.
Alternatively, a polymer of non-linear structure is, for example, a
polymer of branched, star, grafted or other structure may be
used.
[0121] In one embodiment, the film forming polymer polymer
comprises at least three different blocks, and the first and second
blocks of the block polymer are mutually incompatible.
[0122] In one embodiment, the film-forming polymer is an organic
film-forming polymer that is soluble in the fatty phase, which
comprises a liquid phase comprising at least one oil.
[0123] The liposoluble film forming polymer may be of any chemical
type and may especially be chosen from: a) liposoluble, amorphous
homopolymers and copolymers of olefins, of cycloolefins, of
butadiene, of isoprene, of styrene, of vinyl ethers, esters or
amides, or of (meth)acrylic acid esters or amides comprising a
linear, branched or cyclic alkyl group of 4 to 50 carbon atoms, and
which may be amorphous. The liposoluble homopolymers and copolymers
may be obtained from monomers selected from the group consisting of
isooctyl (meth)acrylate, isononyl (meth)acrylate, 2-ethylhexyl
(meth)acrylate, lauryl (meth)acrylate, isopentyl (meth)acrylate,
n-butyl (meth)acrylate, isobutyl (meth)acrylate, methyl
(meth)acrylate, tert-butyl (meth)acrylate, tridecyl (meth)acrylate
and stearyl (meth)acrylate, or combinations thereof.
[0124] Particular liposoluble copolymers that may be used include:
i) acrylic-silicone grafted polymers containing a silicone backbone
and acrylic grafts or containing an acrylic backbone and silicone
grafts, such as the product sold under the name SA 70.5 by 3M and
described in patents U.S. Pat. No. 5,725,882; U.S. Pat. No.
5,209,924; U.S. Pat. No. 4,972,037; U.S. Pat. No. 4,981,903; U.S.
Pat. No. 4,981,902 and U.S. Pat. No. 5,468,477, and in patents U.S.
Pat. No. 5,219,560 and EP 0 388 582; ii) liposoluble polymers
bearing fluoro groups, belonging to one of the classes described
above, in particular the Fomblin products described in patent U.S.
Pat. No. 5,948,393 and the alkyl (meth)acrylate/per-fluoroalkyl
(meth)acrylate copolymers described in patents EP 0 815 836 and
U.S. Pat. No. 5,849,318; iii) polymers or copolymers resulting from
the polymerization or copolymerization of an ethylenic monomer,
comprising one or more ethylenic bonds, which may be conjugated (or
dienes). A s polymers or copolymers resulting from the
polymerization or copolymerization of an ethylenic monomer, it is
possible to use vinyl, acrylic or methacrylic copolymers.
[0125] In one embodiment, the film-forming polymer is a block
copolymer comprising at least one block consisting of styrene units
or styrene derivatives (for example methylstyrene, chlorostyrene or
chloromethylstyrene).
[0126] In one embodiment, the film-forming polymer is selected from
copolymers of a vinyl ester (the vinyl group being directly
attached to the oxygen atom of the ester group and the vinyl ester
having a saturated, linear or branched hydrocarbon-based radical of
1 to 19 carbon atoms, linked to the carbonyl of the ester group)
and of at least one other monomer, which may be a vinyl ester
(other than the vinyl ester already present), an .alpha.-olefin
(containing from 8 to 28 carbon atoms), an alkyl vinyl ether (the
alkyl group of which contains from 2 to 18 carbon atoms) or an
allylic or methallylic ester (containing a saturated, linear or
branched hydrocarbon-based radical of 1 to 19 carbon atoms, linked
to the carbonyl of the ester group).
[0127] These copolymers may be partially crosslinked using
crosslinking agents, which may be either of the vinyl type or of
the allylic or methallylic type, such as tetraallyloxyethane,
divinylbenzene, divinyl octanedioate, divinyl dodecanedioate, and
divinyl octadecanedioate.
[0128] Liposoluble film-forming polymers that may also be mentioned
include liposoluble copolymers, such as those resulting from the
copolymerization of vinyl esters containing from 9 to 22 carbon
atoms or of alkyl acrylates or methacrylates, the alkyl radicals
containing from 10 to 20 carbon atoms.
[0129] Such liposoluble copolymers may be selected from copolymers
of polyvinyl stearate, polyvinyl stearate crosslinked with
divinylbenzene, with diallyl ether or with diallyl phthalate,
polystearyl (meth)acrylate copolymers, polyvinyl laurate and
polylauryl (meth)acrylate copolymers, these poly (meth)acrylates
possibly being crosslinked with ethylene glycol dimethacrylate or
tetraethylene glycol dimethacrylate.
[0130] Amorphous and liposoluble polycondensates, preferably not
comprising any groups donating hydrogen interactions, in particular
aliphatic polyesters containing C4-50 alkyl side chains or
polyesters resulting from the condensation of fatty acid dimers, or
even polyesters comprising a silicone-based segment in the form of
a block, graft or end group, as defined in patent application FR 0
113 920.
[0131] Amorphous and liposoluble polysaccharides comprising alkyl
(ether or ester) side chains, in particular alkylcelluloses
containing a saturated or unsaturated, linear or branched C1 to C8
alkyl radical, such as ethylcellulose and propylcellulose.
[0132] Alternatively, the film-forming polymer may be selected from
cellulose-based polymers such as nitrocellulose, cellulose acetate,
cellulose acetobutyrate, cellulose acetopropionate or
ethylcellulose, or from polyurethanes, acrylic polymers, vinyl
polymers, poly vinyl butyrals, alkyd resins, resins derived from
aldehyde condensation products, such as
arylsulfonamide-formaldehyde resins, for instance
toluenesulfonamide-formaldehyde resin, and aryl sulfonamide epoxy
resins.
[0133] Alternatively, the film forming polymer may be a silicone
resin. For purposes of this application, the term "resin" means a
three-dimensional structure. In one embodiment, the silicone resin
is selected from silsesquioxanes and siloxysilicates. In one
embodiment, the silicone resin is selected from siloxysilicates,
such as trimethyl siloxysilicates, which are represented by the
following formula:
[R.sup.16.sub.3SiO.sub.1/2].sub.E(SiO.sub.4/2).sub.F (units M and
Q), in which subscripts E and F may each independently have values
ranging from 50 to 80, and R.sup.16 represents an alkyl, such as a
methyl or an alkyl of two or more carbon atoms. The ratio of the
units M to the units Q may range from 0.7 to 1.
[0134] Alternatively, the silicone resin may be selected from
silsesquioxanes comprising T units of formula:
[R.sup.17SiO.sub.3/2].sub.G, in which subscript G has a value that
may range up to several thousand and R.sup.17 represents an alkyl,
such as a methyl or an alkyl of two or more carbon atoms. In one
embodiment, the silsesquioxane is selected from
polymethylsilsesquioxanes, which are silsesquioxanes such that
R.sup.17 is a methyl group or a propyl group
(polypropylsilsesquioxane). The polymethylsilsesquioxanes may
comprise, for example, less than 500 T units, and alternatively 50
to 500 T units.
[0135] In one embodiment of the invention, the silicone resin is
soluble or dispersible in silicone oils or volatile organic
liquids. In one embodiment, the silicone resin is solid at
25.degree. C.
[0136] In one embodiment, the silicone resin may have a molecular
mass ranging from 1,000 to 10,000 grams/mol.
[0137] In another embodiment, the film-forming silicone resin is a
copolymer, in which at least one unit of the copolymer is chosen
from the silicone units M, D, T and Q, and in which at least one
additional unit of the copolymer is chosen from esters.
[0138] In a non-limiting manner, the film-forming polymers may be
chosen from the following polymers or copolymers: polyurethanes,
polyurethane-acrylics, polyureas, polyurea-polyurethanes,
polyester-polyure thanes, polyether-polyurethanes, polyesters,
polyesteramides, alkyds; acrylic and/or vinyl polymers or
copolymers; acrylic-silicone copolymers; polyacrylamides; silicone
polymers, for instance silicone polyurethanes or silicone acrylics,
and fluoro polymers, and mixtures thereof.
[0139] The film forming polymer may be a vinyl polymer comprising
at least one carbosiloxane dendrimer-based unit. The vinyl polymer
may especially have a backbone and at least one side chain, which
comprises a carbosiloxane dendrimer structure. For purposes of this
application, the term "carbosiloxane dendrimer structure"
represents a molecular structure with branched groups of high
molecular masses with high regularity in the radial direction
starting from the backbone bond. Such carbosiloxane dendrimer
structures are described in the form of a highly branched
siloxane-silylalkylene copolymer in the laid-open Japanese patent
application Kokai 9-171154.
[0140] The vinyl polymer may be one of the polymers described in
the examples of patent application EP 0 963 751, or a polymer
obtained according to the process described in the said patent
application.
[0141] According to one embodiment, the vinyl polymer may further
comprise at least one organofluorine group. The fluoro vinyl
polymer may be one of the polymers described in the examples of
patent application WO 03/045 337, or one of polymers obtained
according to the process described in said patent application.
[0142] According to one embodiment, the grafted vinyl polymers are
borne in an oil, which is may be volatile, selected from silicone
oils and/or hydrocarbon-based oils. According to one embodiment,
the silicone oil may be cyclopentasiloxane. Alternatively, the
hydrocarbon-based oil may be isododecane. The emulsion may comprise
at least one polyamide polymer or copolymer, which may be selected
from polyamide homopolymers, polyamides branched with fatty chains,
polyamide-organosiloxanes, polyamide-polyester copolymers and
polyamide-polyacrylic copolymers, and mixtures thereof.
[0143] As polyamide polymers that may be used in the emulsion,
mention may also be made of polyamides comprising at least one
polyorganosiloxane group, containing 1 to 1,000 organosiloxane
units in the main chain or in the form of a graft. The polyamide
polymers are, for example, those described in documents U.S. Pat.
No. 5,874,069, U.S. Pat. No. 5,919,444, U.S. Pat. No. 6,051,216,
U.S. Pat. No. 5,981,680 and WO 04/054 524.
[0144] The emulsion may comprise a semi-crystalline polymer, which
may have a melting point of greater than or equal to 30.degree. C.
The melting point values correspond to the melting point measured
using a differential scanning calorimeter (DSC) such as the
calorimeter sold under the name DSC 30 by Mettler, with a
temperature rise of 5 or 10.degree. C. per minute. (The melting
point considered is the point corresponding to the temperature of
the most endothermic peak in the thermogram). The semi-crystalline
polymer comprises at least one crystallizable pendent chain or at
least one crystallizable block. Aside from the crystallizable
chains or blocks, the polymer blocks are amorphous. For the
purposes of the invention, the term "crystallizable chain or block"
means a chain or block which, if it was alone, would change from
the amorphous state to the crystalline state reversibly, depending
on whether it is above or below the melting point. For the purposes
of this application, a chain is a group of atoms that are pendent
or lateral relative to the polymer backbone. A block is a group of
atoms belonging to the backbone, this group constituting one of the
repeating units of the polymer. The semi-crystalline polymers that
may be used in the invention are exemplified by polyolefin block
copolymers of controlled crystallization, the monomers of which are
described in EP-A-0 951 897.
[0145] The film forming polymer, when present, may be in the
emulsion in an amount ranging from 0.1% to 30% by weight.
Additional Surfactants/Emulsifiers
[0146] The emulsion may further comprise an additional surfactant
or emulsifier. The additional surfactant or emulsifier may be solid
at room temperature, which may be a block polymer, a grafted
polymer and/or a random polymer, alone or in combination of two or
more. Among the grafted polymers that may be mentioned are silicone
polymers grafted with a hydrocarbon-based chain and
hydrocarbon-based polymers grafted with a silicone chain.
[0147] Thus, grafted-block or block copolymers comprising at least
one block of polyorganosiloxane type and at least one block of a
free-radical polymer, for instance grafted copolymers of
acrylic/silicone type, may be used, which may be used especially
when the non-aqueous medium contains silicone.
[0148] It is also possible to use grafted-block or block copolymers
comprising at least one block of polyorganosiloxane type and at
least one block of a polyether. The polyorganopolysiloxane block
may be a polydimethylsiloxane or a poly (C2-C18)
alkylmethylsiloxane; the polyether block may be a poly (C2-C18)
alkylene, such as polyoxyethylene and/or polyoxypropylene. In
particular, dimethicone copolyols or (C2-C18) alkyldimethicone
copolyols may be used.
[0149] Water soluble or water dispersible silicone polyether
compositions may be included in the present emulsions. These are
also known as polyalkylene oxide silicone copolymers, silicone poly
(oxyalkylene) copolymers, silicone glycol copolymers, or silicone
surfactants. These can be linear, rake, or graft type materials, or
ABA type where the B is the siloxane polymer block, and the A is
the poly(oxyalkylene) group. The poly(oxyalkylene) group can
consist of polyethylene oxide, polypropylene oxide, or mixed
polyethylene oxide/polypropylene oxide groups. Other oxides, such
as butylene oxide or phenylene oxide are also possible. Another
type of silicone polyether composition that may be included in the
present composition is an ABn polyalkylene oxide silicone
copolymers as described in EP 0 492 657.
[0150] The additional emulsifier or surfactant may be selected from
nonionic, anionic, cationic and amphoteric surfactants or
combinations thereof. Reference may be made to Kirk-Othmer's
"Encyclopedia of Chemical Technology", volume 22, pp. 333-432, 3rd
edition, 1979, Wiley, for the definition of the properties and
(emulsifying) functions of surfactants, in particular pp. 347-377
of this reference, for anionic, amphoteric and nonionic
surfactants.
[0151] Nonionic surfactants may be comprise: oxyethylenated and/or
oxypropylenated ethers (which may comprise from 1 to 150
oxyethylene and/or oxypropylene groups) of glycerol; oxyethylenated
and/or oxypropylenated ethers (which may comprise from 1 to 150
oxyethylene and/or oxypropylene groups) of fatty alcohols
(especially of a C8-C24 and alternatively C12-C18 alcohol), such as
oxyethylenated cetearyl alcohol ether containing 30 oxyethylene
groups (CTFA name Ceteareth-30) and the oxyethylenated ether of the
mixture of C12-C15 fatty alcohols comprising 7 oxyethylene groups
(CTFA name C12-15 Pareth-7); fatty acid esters (such as a C8-C24
and alternatively C16-C22 acid) of polyethylene glycol (which may
comprise from 1 to 150 ethylene glycol units), such as PEG-50
stearate and PEG-40 monostearate; fatty acid esters (especially of
a C8-C24 and preferably C16-C22 acid) of oxyethylenated and/or
oxypropylenated glyceryl ethers (which may comprise from 1 to 150
oxyethylene and/or oxypropylene groups), for instance PEG-200
glyceryl monostearate; glyceryl stearate polyethoxylated with 30
ethylene oxide groups, glyceryl oleate polyethoxy lated with 30
ethylene oxide groups, glyceryl cocoate polyethoxylated with 30
ethylene oxide groups, glyceryl isostearate polyeth oxylated with
30 ethylene oxide groups, and glyceryl laurate polyethoxylated with
30 ethylene oxide groups; fatty acid esters (especially of a C8-C24
and preferably C16-C22 acid) of oxyethylenated and/or
oxypropylenated sorbitol ethers (which may comprise from 1 to 150
oxyethylene and/or oxypropylene groups); dimethicone copolyol
benzoate; copolymers of propylene oxide and of ethylene oxide, also
known as EO/PO polycondensates; and mixtures thereof; saccharide
esters and ethers, such as sucrose stearate, sucrose cocoate and
sorbitan stearate, and mixtures thereof, fatty acid esters (such as
a C8-C24 and alternatively C16-C22 acid) of polyols, especially of
glycerol or of sorbitol, such as glyceryl stearate, glyceryl
stearate, glyceryl laurate, polyglyceryl-2 stearate, sorbitan
tristearate or glyceryl ricinoleate.
[0152] Anionic surfactants include C16-C30 fatty acid salts, such
as those derived from amines, for instance triethanolamine
stearate; polyoxyethylenated fatty acid salts, such asthose derived
from amines or alkali metal salts, and combinations thereof;
phosphoric esters and salts thereof, such as DEA oleth-10 phosphate
or monocetyl monopotassium phosphate sulf osuccinates such as
Disodium PEG-5 citrate lauryl sulf osuccinate and Disodium
ricinoleamido MEA sulf osuccinate; alkyl ether sulfates, such as
sodium lauryl ether sulfate; isethionates; acylglutamates such as
disodium hydrogenated tallow glutamate, alkyl polyglucosides and
combinations thereof.
[0153] The emulsion may further comprise an amphoteric surfactant,
for instance N-acylamino acids such as N-alkylaminoacetates and
disodium cocoamphodiacetate, and amine oxides such as stearamine
oxide, or alternatively silicone surfactants, for instance
dimethicone copolyol phosphates.
Dyestuffs
[0154] The emulsion may further comprise a dyestuff. The dyestuff
may be selected from pulverulent dyestuffs (such as pigments and
nacres) and water-soluble dyestuffs. For purposes of this
application, the term "pigments" means white or colored, mineral or
organic particles of any form, which are insoluble in the
physiological medium, and which are intended to color the emulsion.
For purposes of this application, the term "nacres" means
iridescent particles of any form, produced especially by certain
molluscs in their shell, or else synthesized.
[0155] The pigments may be white or colored, and mineral and/or
organic. The mineral pigments include titanium dioxide, optionally
surface-treated, zirconium oxide or cerium oxide, zinc oxide, iron
oxide (black, yellow or red), chromium oxide, manganese violet,
ultramarine blue, chromium hydrate, ferric blue, and metal powders,
for instance aluminum powder or copper powder. The organic pigments
include carbon black, pigments of D & C type, and lakes based
on cochineal carmine or on barium, strontium, calcium or
aluminum.
[0156] Mention may also be made of pigments with an effect, such as
particles comprising a natural or synthetic, organic or mineral
substrate, for example glass, acrylic resins, polyester,
polyurethane, polyethylene terephthalate, ceramics or aluminas,
said substrate being uncoated or coated with metallic substances,
for instance aluminum, gold, silver, platinum, copper or bronze, or
with metal oxides, for instance titanium dioxide, iron oxide or
chromium oxide, and combinations thereof.
[0157] The nacres may be chosen from white nacreous pigments such
as mica coated with titanium or with bismuth oxychloride, colored
nacreous pigments such as titanium mica coated with iron oxides,
titanium mica coated with ferric blue or with chromium oxide,
titanium mica coated with an organic pigment of the abovementioned
type, and also nacreous pigments based on bismuth oxychloride.
Interference pigments, such as liquid-crystal or multilayer
interference pigments, may alternatively be used.
Structuring Agents
[0158] The emulsion may further comprise a structuring agent. For
purposes of this application, the term "structuring agent" means a
compound capable of increasing the viscosity of the emulsion. The
structuring agent makes it possible to obtain an emulsion that can
have a texture ranging from fluid to solid textures.
[0159] The structuring agent may be present in the emulsion in an
amount ranging from 0.1% to 20% by weight, alternatively ranging
from 0.1% to 15% by weight and alternatively ranging from 0.5% to
10% by weight, relative to the total weight of the emulsion.
[0160] The structuring agent may be selected from thickeners
(oily-medium thickeners; aqueous-medium thickeners), organogelling
agents, waxes, pasty compounds and gums.
[0161] The aqueous-medium thickener may be chosen from: hydrophilic
clays, hydrophilic fumed silica, water-soluble cellulose-based
thickeners, guar gum, xanthan gum, carob gum, scleroglucan gum,
gellan gum, rhamsan gum, karaya gum or carrageenan gum, alginates,
maltodextrins, starch and its derivatives, and hyaluronic acid and
its salts, the polyglyceryl (meth)acrylate polymers sold under the
names Hispagel or Lubragel by Hispano Quimica or Guardian,
polyvinylpyrrolidone, polyvinyl alcohol, crosslinked acrylamide
polymers and copolymers, or alternatively the crosslinked
methacryloyloxyethyltrimethylammonium chloride homopolymers,
associative polymers and especially associative polyurethanes and
sodium acrylate blends. Such thickeners are described especially in
patent application EP-A-1 400 234.
[0162] The oily-medium thickener may be chosen from: organophilic
clays; hydrophobic fumed silicas; alkyl guar gums (with a C1-C6
alkyl group), such as those described in EP-A-708 114; oil-gelling
polymers, for instance triblock polymers or star polymers resulting
from the polymerization or copolymerization of at least one monomer
containing an ethylenic group.
[0163] Alternatively, the structuring agent can be a wax. For the
purposes of this application, the term "wax" means a lipophilic
compound that is solid at room temperature (25.degree. C.), which
undergoes a reversible solid/liquid change of state, and which has
a melting point of greater than or equal to 30.degree. C., which
may be up to 120.degree. C.
[0164] The waxes may be hydrocarbon-based waxes, fluoro waxes
and/or silicone waxes, and may be of plant, mineral, animal and/or
synthetic origin. In particular, the waxes may have a melting point
of greater than 30.degree. C.
[0165] Suitable waxes include beeswax, carnauba wax or candelilla
wax, paraffin, microcrystalline waxes, ceresin or ozokerite;
synthetic waxes, for instance polyethylene waxes or Fischer-Tropsch
waxes, and silicone waxes, for instance alkyl, alkoxy dimethicones
containing from 16 to 45 carbon atoms or silsesquioxane resin wax
as described in patent application publication WO2005100444.
[0166] Alternatively, the emulsion may contain a pasty compound,
which may be selected from lanolin and its derivatives; polymeric
or non-polymeric silicone compounds; polymeric or non-polymeric
fluoro compounds; vinyl polymers, such as olefin homopolymers,
olefin copolymers, hydrogenated diene homopolymers, and linear or
branched oligomers, homopolymers or copolymers of alkyl
(meth)acrylates, such as those containing a C8-C30 alkyl group;
oligomers, homopolymers, and copolymers of vinyl esters containing
C8-C30 alkyl groups; oligomers, homopolymers and copolymers of
vinyl ethers containing C8-C30 alkyl groups; liposoluble polyethers
resulting from the polyetherification between one or more C2-C100
(alternatively C2-C50) diols, esters, and combinations thereof. The
esters include esters of a glycerol oligomer, especially diglycerol
esters, in particular condensates of adipic acid and of glycerol,
for which some of the hydroxyl groups of the glycerols have reacted
with a mixture of fatty acids such as stearic acid, capric acid,
stearic acid and isostearic acid, and 12-hydroxystearic acid. The
pasty compounds of plant origin include a mixture of soybean
sterols and of oxyethylenated (5 OE) oxypropylenated (5 OP)
pentaerythritol.
Active Ingredients
[0167] As used herein, a "personal care active" means any compound
or combination of compounds that are known in the art as additives
in the personal care formulations that are typically added for the
purpose of treating hair or skin to provide a cosmetic and/or
aesthetic benefit. A "healthcare active" means any compound or
mixtures of compounds that are known in the art to provide a
pharmaceutical or medical benefit. Thus, "healthcare active"
include materials consider as an active ingredient or active drug
ingredient as generally used and defined by the United States
Department of Health & Human Services Food and Drug
Administration, contained in Title 21, Chapter I, of the Code of
Federal Regulations, Parts 200-299 and Parts 300-499.
[0168] Some representative examples of active ingredients include;
drugs, vitamins, minerals; hormones; topical antimicrobial agents
such as antibiotic active ingredients, antifungal active
ingredients for the treatment of athlete's foot, jock itch, or
ringworm, and acne active ingredients; astringent active
ingredients; deodorant active ingredients; wart remover active
ingredients; corn and callus remover active ingredients;
pediculicide active ingredients for the treatment of head, pubic
(crab), and body lice; active ingredients for the control of
dandruff, seborrheic dermatitis, or psoriasis; and sunburn
prevention and treatment agents.
[0169] Useful active ingredients for use in the emulsion include
vitamins and their derivatives, including "pro-vitamins". Vitamins
useful herein include, but are not limited to, Vitamin A.sub.1,
retinol, C2 to C18 esters of retinol, vitamin E, tocopherol, esters
of vitamin E, and combinations thereof. Retinol includes
trans-retinol, 1,3-cis-retinol, 11-cis-retinol, 9-cis-retinol, and
3,4-didehydro-retinol, Vitamin C and its derivatives, Vitamin
B.sub.1, Vitamin B.sub.2, Pro Vitamin B5, panthenol, Vitamin
B.sub.6, Vitamin B.sub.12, niacin, folic acid, biotin, and
pantothenic acid. Other suitable vitamins and the International
Nomenclature Cosmetic Ingredient Name (INCI) names for the vitamins
considered included herein are ascorbyl dipalmitate, ascorbyl
methylsilanol pectinate, ascorbyl palmitate, ascorbyl stearate,
ascorbyl glucocide, sodium ascorbyl phosphate, sodium ascorbate,
disodium ascorbyl sulfate, potassium (ascorbyl/tocopheryl)
phosphate.
[0170] Alternatively, the active ingredient used in the emulsion
can be an active drug ingredient. Representative examples of some
suitable active drug ingredients which can be used are
hydrocortisone, ketoprofen, timolol, pilocarpine, adriamycin,
mitomycin C, morphine, hydromorphone, diltiazem, theophylline,
doxorubicin, daunorubicin, heparin, penicillin G, carbenicillin,
cephalothin, cefoxitin, cefotaxime, 5-fluorouracil, cytarabine,
6-azauridine, 6-thioguanine, vinblastine, vincristine, bleomycin
sulfate, aurothioglucose, suramin, mebendazole, clonidine,
scopolamine, propranolol, phenylpropanolamine hydrochloride,
ouabain, atropine, haloperidol, isosorbide, nitroglycerin,
ibuprofen, ubiquinones, indomethacin, prostaglandins, naproxen,
salbutamol, guanabenz, labetalol, pheniramine, metrifonate, and
steroids.
[0171] Considered to be included herein as active drug ingredients
for purposes of this application are antiacne agents such as
benzoyl peroxide and tretinoin; antibacterial agents such as
chlorohexadiene gluconate; antifungal agents such as miconazole
nitrate; anti-inflammatory agents; corticosteroidal drugs;
non-steroidal anti-inflammatory agents such as diclofenac;
antipsoriasis agents such as clobetasol propionate; anesthetic
agents such as lidocaine; antipruritic agents; antidermatitis
agents; and agents generally considered barrier films.
[0172] Alternatively, the active ingredient in the emulsion can be
a protein, such as an enzyme. Enzymes include, but are not limited
to, commercially available types, improved types, recombinant
types, wild types, variants not found in nature, and mixtures
thereof. For example, suitable enzymes include hydrolases,
cutinases, oxidases, transferases, reductases, hemicellulases,
esterases, isomerases, pectinases, lactases, peroxidases, laccases,
catalases, and mixtures thereof. Hydrolases include, but are not
limited to, proteases (bacterial, fungal, acid, neutral or
alkaline), amylases (alpha or beta), lipases, mannanases,
cellulases, collagenases, lisozymes, superoxide dismutase,
catalase, and mixtures thereof. Said proteases include, but are not
limited to, trypsin, chymotrypsin, pepsin, pancreatin and other
mammalian enzymes; papain, bromelain and other botanical enzymes;
subtilisin, epidermin, nisin, naringinase(L-rhammnosidase)
urokinase and other bacterial enzymes. Said lipases include, but
are not limited to, triacyl-glycerol lipases, monoacyl-glycerol
lipases, lipoprotein lipases, e.g., steapsin, erepsin, pepsin,
other mammalian, botanical, bacterial lipases and purified ones.
Natural papain is useful as said enzyme. Further, stimulating
hormones, e.g., insulin, can be used together with these enzymes to
boost the effectiveness of them.
[0173] Alternatively, the active ingredient may be a sunscreen
agent. The sunscreen agent can be selected from any sunscreen agent
known in the art to protect skin from the harmful effects of
exposure to sunlight. The sunscreen agent may be selected from an
organic compound, an inorganic compound, or a combination thereof
that absorbs ultraviolet (UV) light. Representative, non-limiting
examples that can be used as the sunscreen agent include;
Aminobenzoic Acid, Cinoxate, Diethanolamine Methoxycinnamate,
Digalloyl Trioleate, Dioxybenzone, Ethyl 4-[bis(Hydroxypropyl)]
Aminobenzoate, Glyceryl Aminobenzoate, Homosalate, Lawsone with
Dihydroxyacetone, Menthyl Anthranilate, Octocrylene, Octyl
Methoxycinnamate, Octyl Salicylate, Oxybenzone, Padimate O,
Phenylbenzimidazole Sulfonic Acid, Red Petrolatum, Sulisobenzone,
Titanium Dioxide, and Trolamine Salicylate, cetaminosalol, Allatoin
PABA, Benzalphthalide, Benzophenone, Benzophenone 1-12,
3-Benzylidene Camphor, Benzylidenecamphor Hydrolyzed Collagen
Sulfonamide, Benzylidene Camphor Sulfonic Acid, Benzyl Salicylate,
Bornelone, Bumetriozole, Butyl Methoxydibenzoylmethane, Butyl PABA,
Ceria/Silica, Ceria/Silica Talc, Cinoxate, DEA-Methoxycinnamate,
Dibenzoxazol Naphthalene, Di-t-Butyl Hydroxybenzylidene Camphor,
Digalloyl Trioleate, Diisopropyl Methyl Cinnamate, Dimethyl PABA
Ethyl Cetearyldimonium Tosylate, Dioctyl Butamido Triazone,
Diphenyl Carbomethoxy Acetoxy Naphthopyran, Disodium Bisethylphenyl
Tiamminotriazine Stilbenedisulfonate, Disodium Distyrylbiphenyl
Triaminotriazine Stilbenedisulfonate, Disodium Distyrylbiphenyl
Disulfonate, Drometrizole, Drometrizole Trisiloxane, Ethyl
Dihydroxypropyl PABA, Ethyl Diisopropylcinnamate, Ethyl
Methoxycinnamate, Ethyl PABA, Ethyl Urocanate, Etrocrylene Ferulic
Acid, Glyceryl Octanoate Dimethoxycinnamate, Glyceryl PABA, Glycol
Salicylate, Homosalate, Isoamyl p-Methoxycinnamate, Isopropylbenzyl
Salicylate, Isopropyl Dibenzolylmethane, Isopropyl
Methoxycinnamate, Menthyl Anthranilate, Menthyl Salicylate,
4-Methylbenzylidene, Camphor, Octocrylene, Octrizole, Octyl
Dimethyl PABA, Octyl Methoxycinnamate, Octyl Salicylate, Octyl
Triazone, PABA, PEG-25 PABA, Pentyl Dimethyl PABA,
Phenylbenzimidazole Sulfonic Acid, Polyacrylamidomethyl Benzylidene
Camphor, Potassium Methoxycinnamate, Potassium Phenylbenzimidazole
Sulfonate, Red Petrolatum, Sodium Phenylbenzimidazole Sulfonate,
Sodium Urocanate, TEA-Phenylbenzimidazole Sulfonate,
TEA-Salicylate, Terephthalylidene Dicamphor Sulfonic Acid, Titanium
Dioxide, Zinc Dioxide, Serium Dioxide, TriPABA Panthenol, Urocanic
Acid, and VA/Crotonates/Methacryloxybenzophenone-1 Copolymer. These
sunscreen agents can be selected as one or a combination of two or
more.
[0174] Alternatively, the active ingredient may a plant extract.
Alternatively, the active ingredient may be a self tanning agent
such as but not limited to dihydroxyacetone and erythrulose or an
insect repellent such as but not limited to ethyl
butylacetylaminopropionate or plant extract such as citronella. The
amount of active ingredient present in the emulsion will vary
depending on factors including the type of active ingredient
selected and the method of use of the emulsion, however, the amount
of active ingredient may range from 0.05 wt % to 50 wt %,
alternatively 1 wt % to 25 wt %, or alternatively 1 to 10 wt %,
based on the weight of the emulsion.
[0175] Alternatively, the active ingredient may be an
antiperspirant and/or deodorant agent. Some examples of
antiperspirant agents and deodorant agents are Aluminum Chloride,
Aluminum Zirconium Tetrachlorohydrex GLY, Aluminum Zirconium
Tetrachlorohydrex PEG, Aluminum Chlorohydrex, Aluminum Zirconium
Tetrachlorohydrex PG, Aluminum Chlorohydrex PEG, Aluminum Zirconium
Trichlorohydrate, Aluminum Chlorohydrex PG, Aluminum Zirconium
Trichlorohydrex GLY, Hexachlorophene, Benzalkonium Chloride,
Aluminum Sesquichlorohydrate, Sodium Bicarbonate, Aluminum
Sesquichlorohydrex PEG, Chlorophyllin-Copper Complex, Triclosan,
Aluminum Zirconium Octachlorohydrate, and Zinc Ricinoleate.
Fragrance
[0176] Fragrance or perfume can also be added to the emulsion. The
fragrance can be any perfume or fragrance ingredient commonly used
in the perfume industry. These fragrance ingredients may belong to
a variety of chemical classes, as varied as alcohols, aldehydes,
ketones, esters, ethers, acetates, nitrites, terpenic hydrocarbons,
heterocyclic nitrogen or sulfur containing compounds, as well as
essential oils of natural or synthetic origin. Many of these
fragrance ingredients are described in detail in standard textbook
references such as Perfume and Flavour Chemicals, 1969, S.
Arctander, Montclair, N.J.
Preservatives
[0177] When making an emulsion with the emulsifiers described
herein, it may be desirable to add various preservatives such as
the parabens, BHT, BHA, phenoxy ethanol, as listed on the Annex VI,
Part 1 of the European Cosmetic directive--LIST OF PRESERVATIVES
WHICH COSMETIC PRODUCTS MAY CONTAIN. When present, the amount of
preservative may range from 0.01% to 5% by weight based on the
weight of the emulsion.
[0178] The emulsion is suitable for use in personal care products.
Such personal care products are exemplified by antiperspirants and
deodorants, skin creams, skin care lotions, moisturizers, facial
treatments such as acne or wrinkle removers, personal and facial
cleansers, bath oils, perfumes, colognes, sachets, sunscreens,
pre-shave and after-shave lotions, shaving soaps, and shaving
lathers, hair shampoos, hair conditioners, hair colorants, hair
relaxants, hair sprays, mousses, gels, permanents, depilatories,
and cuticle coats, make-ups, color cosmetics, foundations,
concealers, blushes, lipsticks, eyeliners, mascara, oil removers,
color cosmetic removers, wrinkle fillers, skin imperfection hiders,
skin surface smoothers, eyelash curlers, nail varnishes, hair
make-up products, eye shadows, body makeups, and powders,
medicament creams, pastes or sprays including anti-acne, dental
hygienic, antibiotic, healing promotive, nutritive and the like,
which may be preventative and/or therapeutic.
EXAMPLES
[0179] The following examples are included to demonstrate the
invention to one of ordinary skill However, those of ordinary skill
in the art should, in light of the present disclosure, appreciate
that many changes can be made in the specific embodiments which are
disclosed and still obtain a like or similar result without
departing from the spirit and scope of the invention. All amounts,
ratios, and percentages are by weight unless otherwise
indicated.
Reference Example 1A
Long Chain Copolymer Synthesis
[0180] In a 1000 ml glass reactor equipped with stirrer,
temperature controller, and reflux condenser the copolymer was
prepared by first reacting 125 g trimethylsiloxy terminated
poly(dimethyl/methyl(aminoethylaminoisobutyl)siloxane), with a DP
of 380 and 8 to 10 aminoethylaminoisobutyl groups per molecule with
3.57 g of gluconolactone, which was an amount sufficient to react
with half of the primary amines on the
poly(dimethyl/methyl(aminoethylaminoisobutyl)siloxane). This
reaction was performed in the presence of 129 g ethanol at a
temperature of 74.degree. C. In a second step, the resulting
polymer was reacted with a mixture of dodecylglycidyl ether and
tetradecylgycidyl ether. This second step reaction was also carried
out in the presence of ethanol at 74.degree. C.
[0181] After the completion of the reaction, 385.7 g of Isopropyl
Myristate emollient was added to the reaction mixture, then the
ethanol solvent was stripped out at a temperature of 74.degree. C.
under full vacuum.
Reference Example 1B
Long Chain Copolymer Synthesis
[0182] In a 1000 ml glass reactor equipped with stirrer,
temperature controller, and reflux condenser the copolymer was
prepared by first reacting 125 g trimethylsiloxy terminated
poly(dimethyl/methyl(aminoethylaminoisobutyl)siloxane), with a DP
of 380 and 8 to 10 aminoethylaminoisobutyl groups per molecule with
3.57 g of gluconolactone, which was an amount sufficient to react
with half of the primary amines on the
poly(dimethyl/methyl(aminoethylaminoisobutyl)siloxane). This
reaction was performed in the presence of 129 g ethanol at a
temperature of 74.degree. C. In a second step, the resulting
polymer was reacted with a mixture of dodecylglycidyl ether and
tetradecylgycidyl ether. This second step reaction was also carried
out in the presence of ethanol at 74.degree. C.
[0183] After the completion of the reaction, 385.7 g of 5 cSt 200
Fluid emollient was added to the reaction mixture, then the ethanol
solvent was stripped out at a temperature of 74.degree. C. under
full vacuum. The reaction scheme was as follows for the second step
in both reference 1A and 1B:
##STR00004##
[0184] In the reaction scheme, subscript y was 8 to 10 and
subscript x had a value sufficient to give the copolymer a DP of
350 to 400. Proton Nuclear Magnetic Resonance (H-NMR) was used to
confirm the structure in the reaction scheme above.
Reference Example 2
H-NMR
[0185] H-NMR was used to confirm the completion of reaction. For
each copolymer tested, 0.2 g of sample was weighed into a small
vial, and 0.175 g of CD3OD (Aldrich) and 2.5-2.7 g of CDCl.sub.3
containing 0.03% toluene were added to the vial containing the
sample and mixed until miscible. Proton NMR spectra were generated
using a Varian Mercury 300 MHz spectrometer. Functional group
concentrations were obtained by peak integration of both the
characteristic sample peaks and the toluene internal standard. The
aldonamide proton on the carbon adjacent to the carbonyl was used
to determine the aldonamide concentration by using an internal
standard.
Reference Example 3
Short Chain Copolymer Synthesis
[0186] A copolymer was prepared as in Reference Example 1, except
that a trimethylsiloxy terminated
poly(dimethyl/methyl(aminoethylaminoisobutyl)siloxane), with a DP
of 44 was used instead of the
poly(dimethyl/methyl(aminoethylaminoisobutyl)siloxane) of Reference
Example 1. In a 500 ml flask that was equipped with stirrer, reflux
condenser, and temperature controller, 100 g of trimethylsiloxy
terminated poly(dimethyl/methyl(aminoethylaminoisobutyl)siloxane),
with a DP of 44 and an average 2.57 of aminoethylaminoisobutyl
functional groups per molecule and 6.61 g of delta-gluconolactone
were added. Then 106.6 g of Ethanol was added, and the mixture was
reacted at 74.degree. C. After four hours of reaction, 40.12 g of
dodecyl/tetradecyl glycidyl ether was added and reacted for 8
hours. At the completion of the reaction ethanol was removed by
stripping at 74.degree. C. at full vacuum.
[0187] The reaction scheme of the second step was as follows.
##STR00005##
[0188] H-NMR as described in Reference Example 2 was used to
confirm the structure in the reaction scheme above.
Examples 1 and 2 and Comparative Example 1
[0189] The copolymers prepared in Reference Example 1 and Reference
Example 3 were dispersed in various oils to determine
compatibility. For comparative purposes a commercially available
copolymer, ABIL.RTM. EM 90 a cetyl polyethylene glycol,
polypropylene glycol functional polydimethylsiloxane from Evonik
Goldschmidt Corporation of Hopewell, Va., U.S.A.
[0190] These emulsifiers were dispersed in the oils. In each
sample, 9 grams of oil and 1 g of copolymer were mixed under
ambient conditions. The results are in Table 1.
TABLE-US-00001 TABLE 1 Compatibility Test Results Example
Comparative 1 2 Example 1 Copolymer Copolymer of Copolymer of
Reference Reference Oil Example 1B Example 3 Abil 90 EM 5 cSt 200
Fluid clear slightly hazy hazy FZ-3196 clear clear clear
Isohexadecane clear clear clear Isopropyl Myristate clear clear
clear Alkyl Benzoate immiscible slightly hazy clear Capric
Triglyceride immiscible hazy clear Mineral Oil immiscible hazy
clear
[0191] In Table 1, 5 cSt 200 Fluid refers to a polydimethylsiloxane
having viscosity of 5 cSt available from Dow Corning Corporation as
DOW CORNING.RTM. 200 Fluid, and FZ-3196 refers to a
polydialkylsiloxane fluid available from Dow Corning
Corporation.
Emulsion Examples 3-6 and Comparative Emulsion Examples 2-5
[0192] Oil phase samples were prepared by dispersing the copolymer
of Reference Example 1 (shown as the product of the reaction
scheme) and the copolymer of Reference Example 3 (shown as the
product of the reaction scheme) in a silicone oil (5 cSt 200 Fluid,
polydimethylsiloxane) and in an organic oil (isopropyl myristate).
In each oil phase sample, 1 g of copolymer, 18 g of oil and 1 g
absolute ethanol were mixed at ambient temperature overnight. For
comparative purposes, the intermediates prepared in Reference
Example 1 and Reference Example 3 (each shown as the first
structure in the reaction schemes) were formulated into comparative
oil phase samples. In each comparative oil phase sample, 1 g of
intermediate, 18 g of oil and 1 g absolute ethanol were mixed at
ambient temperature overnight. The results of the dispersion to
prepare oil phase samples are shown in Table 1. The oil phase
samples prepared using the copolymers of Reference Examples 1 and 3
formed clear solutions. The oil phase samples of the intermediates
of Reference Examples 1 and 3 formed hazy mixtures when 5 cSt
polydimethylsiloxane oil was used, and the oil phase samples of the
intermediates of Reference Examples 1 and 3 did not mix when
isopropyl myristate was used.
[0193] Samples of aqueous phase were prepared by adding 2 g NaCl to
78 g deionized water. The mixture was stirred until a clear
solution was obtained.
[0194] Emulsion samples were prepared by adding 5 g increments of
the aqueous phase to each of the 20 g oil phase samples. After each
addition, the composition was mixed with a SpeedMixer from FlackTek
at 3400 rpm for 50 seconds. A total of 80 g water phase was added
to each oil phase sample using this procedure. The results are in
Table 2.
TABLE-US-00002 TABLE 2 Comparative Comparative Comparative
Comparative Example 3 Example 4 Example 5 Example 6 Example 2
Example 3 Example 4 Example 5 Emulsifier Copolymer Copolymer
Copolymer Copolymer Intermediate Intermediate Intermediate
Intermediate of RE 1B of RE 1A of RE 3 of RE3 of RE1B of RE1A of
RE3 of RE3 Average chain length 380 380 44 44 380 380 44 44 of
emusifier Chain length/pendant 43.3 43.3 17.2 17.2 43.3 43.3 17.2
17.2 group ratio of emulsifier C12/C14-Alkyl to 3 3 3 3 0 0 0 0
Sugar ratio Oil 5 cSt IPM 5 cSt IPM 5 cSt IPM 5 cSt IPM 200 fl. 200
fl. 200 fl. 200 fl. Dispersion result clear clear clear clear
slightly not slightly not solution solution solution solution hazy
mixing hazy mixing Emulsification result w/o w/o w/o w/o w/o no w/o
no emulsion emulsion emulsion emulsion emulsion emulsion emulsion
emulsion
[0195] IPM refers to isopropyl myristate, and 5 cSt 200 fl. Refers
to a polydimethylsiloxane having viscosity of 5 cSt available from
Dow Corning Corporation as DOW CORNTNG.RTM. 200 Fluid. RE1A refers
to Reference Example 1A. RE1B refers to Reference Example 1B. RE3
refers to Reference Example 3. W/O emulsion means that a water in
oil emulsion formed.
Emulsification Procedure
[0196] Water in oil emulsion samples were prepared according to the
following general procedure. The oil phase was prepared by mixing
an emulsifier with an oil. The oil was isopropyl myristate or DOW
CORNING.RTM. 200 Fluid, a silicone oil with a viscosity of 5 cSt,
which is commercially available from Dow Corning Corporation. The
emulsifier was a copolymer as described above or a comparative
emulsifier. In each 20 gram (g) sample of oil phase, the oil phase
contained 2 g emulsifier and 18 g oil.
[0197] The aqueous phase was prepared by mixing water and sodium
chloride in a water:NaCl weight ratio ranging from 39:1 to 99:1.
For each sample, 80 g of aqueous phase was prepared.
[0198] For each sample, the aqueous phase was added to the oil
phase in 5 g increments. Between the addition of each increment,
the sample was mixed for 40 seconds (s) at 3400 revolutions per
minute (rpm) in a DAC150 FlackTek.TM. SpeedMixer.TM. (commercially
available from FlackTek, Inc. of Landrum, S.C., U.S.A.) to provide
a coarse emulsion.
[0199] After all the aqueous phase was added, the resulting coarse
emulsion was subjected to shear at .gtoreq.7,000 rpm in a
homogenizer (T25 Digital ULTRA-TURRAX.RTM. commercially available
from IKA of Wilmington, N.C., U.S.A.) to provide the final emulsion
sample.
Reference Example 4
Process for Making an Emulsion with Stirrer Mixer
[0200] Emulsions containing the ingredients in Tables 3, 5, and 7
using the copolymer as emulsifier were prepared by the following
method:
1. The ingredients of phase A were mixed together to obtain a
homogeneous mix. 2. The ingredients of phase B were mixed together
to obtain a homogeneous mix 3. Phase B was added to phase A under
mixing (with a cross stirrer). While adding phase B, mixing speed
increased from 700 rpm to 1000 rpm. 4. After all phase B was added,
the resulting product was mixed for 1 minute at 1000 rpm and 5
minutes at 2000 rpm. A coarse emulsion was obtained. 5. A 100 gram
sample of the coarse emulsion was passed through a high shear
mixing apparatus for 15 seconds to reduce the particle size. The
high shear mixing apparatus was a lab mixer from Silverson Machines
Ltd. of England. A fine emulsion was obtained.
Reference Example 5
Emulsion Stability
[0201] Stability of the emulsions 7-29 prepared herein was
evaluated during storage of samples of each emulsion for 6 months
at room temperature (RT), 40.degree. C., and 50.degree. C.
Stability was measured by visual inspection. The results are in
Tables 4, 6, and 8 below.
Reference Example 6
Freeze/Thaw Stability of Emulsions
[0202] Samples of the emulsions 7-29 prepared herein were evaluated
for freeze/thaw stability. The procedure was as follows:
1. Emulsion samples were refrigerated at 4.degree. C. for a minimum
of 12 hours and then stored at RT for few hours. 2. Emulsion
stability was evaluated. Stability was measured by visual
inspection. 3. Steps 1 and 2 were repeated five times. The results
are in Tables 4, 6, and 8 below.
TABLE-US-00003 TABLE 3 Emulsion Samples prepared with a stirrer
mixer Sample Number 7 8 9 10 11 12 13 Ingredient % % % % % % %
Phase A Copolymer of Reference 1 1 2 2 2 1 1 (oil) Example 3
Xiameter .RTM. PMX-200 Silicone / / / / 18 / / Fluid 5CS Xiameter
.RTM. PMX-Silicone 200 19 / 18 / / 9 39 Fluid 5CS/Crodamol GTCC
(50%/50% mixture) Mineral Oil / 19 / 18 / / / Phase B Water 74 74
74 74 74 84 54 (aqueous) Glycerin 5 5 5 5 5 5 5 NaCl 1 1 1 1 1 1
1
In the tables, Crodamol GTCC refers to a medium chain triglyceride
of low viscosity, which is used as an emollient. Crodamol GTCC is
commercially available from Croda, Inc. of Edison, New jersey,
U.S.A.
TABLE-US-00004 TABLE 4 Results of Evaluation of Emulsions in Table
3 Viscosity (Brookfield DV-II-Spindle 6, 2.5 rpm) 1 day 38400 /
50800 151000 115000 / 3200 1 week 46000 / 71000 133000 104000 /
3200 2 weeks 32000 / 74800 108000 106000 / 3200 3 weeks 15200 /
74400 104000 98700 / 2800 1 month 16400 / 72800 108000 85200 / 2800
2 months / / 74800 84800 / / / 3 months / / 69200 82000 / / / 4
months / / 66800 75600 / / / Stability At RT stable almost broken
stable stable stable for broken after stable for at least after
high at least at least 2 months high shear 4 weeks 3 months shear
mixing- 4 months 4 months mixing Broken after 1 day At 40.degree.
C. stable for / stable stable for stable for / / 2 months at least
4 weeks 4 weeks 4 months At 50.degree. C. stable for / stable for
stable stable for / stable for 3 weeks 3 weeks at least 3 weeks 2
weeks 4 months F/T Cycle 0 / 0 0 0 / at least 4 cycles Sample 7 8 9
10 11 12 13
TABLE-US-00005 TABLE 5 Emulsion Samples prepared with a stirrer
mixer Sample Number 14 15 16 17 18 19 20 21 Ingredient % % % % % %
% % Phase A Copolymer of Reference 4 4 8 8 8 4 4 8 Example 1A
Xiameter .RTM. PMX-200 Silicone / / / / 12 / / / Fluid 5 cSt
Xiameter .RTM. PMX-Silicone 200 16 / 12 / / 6 36 32 Fluid 5 cSt
Crodamol GTCC (50%/50% mixture) Mineral Oil / 16 / 12 / / / / Phase
B Water 74 74 74 74 74 84 54 54 Glycerin 5 5 5 5 5 5 5 5 NaCl 1 1 1
1 1 1 1 1
TABLE-US-00006 TABLE 6 Results of Evaluation of Emulsions in Table
5 Viscosity (Brookfield DV-II-Spindle 6, 2.5 rpm) (cP) 1 day 190000
148000 74400 112000 214000 / 14000 16200 1 week 184000 80000 78400
78000 188000 / 10400 14700 2 weeks 204000 83000 81200 61000 187000
/ / / 3 weeks / / 82800 57000 179000 / / / 1 month 213000 133000
81000 45200 183000 / / / 2 months / / 84400 44400 18700 / / / 3
months / / 80400 38000 180000 / / / 4 months / / 72000 / 166000 / /
/ Stability At RT stable stable stable stable for stable Broken
stable for stable for at least at least at least 3 months at least
during the 1 week 1 week 3 months 3 months 4 months 4 months
process At 40.degree. C. stable for stable stable stable for stable
/ stable for stable for 2 months at least at least 3 weeks at least
1 week 1 week 3 months 4 months 4 months At 50.degree. C. stable
for stable stable for stable for stable / stable for stable for 3
months at least 4 weeks 3 months at least 1 week 1 week 3 months 4
months F/T Cycle 1 cycle 0 0 0 5 cycles / 0 0 Sample 14 15 16 17 18
19 20 21
TABLE-US-00007 TABLE 7 Emulsion Samples prepared with a stirrer
mixer Sample Number 22 23 24 25 26 27 28 29 Ingredient % % % % % %
% % Phase A Copolymer of Reference 4 4 8 8 8 4 4 8 Example 1B
Xiameter .RTM. PMX-200 / / / / 12 / / / Silicone Fluid 5 cSt
Xiameter .RTM. PMX-Silicone 16 / 12 / / 6 36 32 200 Fluid 5 cSt/
Crodamol GTCC (50%/50%) Mineral Oil / 16 / 12 / / / / Phase B Water
74 74 74 74 74 84 54 54 Glycerin 5 5 5 5 5 5 5 5 NaCl 1 1 1 1 1 1 1
1
TABLE-US-00008 TABLE 8 Results of Evaluation of Emulsions in Table
7 Viscosity (Brookfield DV-II-Spindle 6, 2.5 rpm) (cP) 1 day 105000
/ 236000 195000 143000 / 9200 16600 1 week 106000 / 234000 136000
127000 / 5600 15500 2 weeks 102000 / 206000 95600 130000 / / / 3
weeks / / 20400 82700 131000 / / / 1 month / / 20500 84800 120000 /
/ / 2 months / / 195000 84000 120000 / / / 3 months / / 185000
78800 112000 / / / 4 months / / 147000 75200 / / / Stability At RT
stable broken stable stable stable Impossible stable for stable for
at least after high at least at least at least to 1 week 1 week 3
months shear 4 months 4 months 3 months emulsify mixing At
40.degree. C. stable for / stable for stable stable / stable for
stable for 2 months 2 months at least at least 1 week 1 week 4
months 3 months At 50.degree. C. stable for / / stable stable for /
stable for stable for 1 month at least 1 month 1 week 1 week 4
months F/T Cycle 1 cycle / 5 0 1 / 0 0 Sample 22 23 24 25 26 27 28
29
INDUSTRIAL APPLICABILITY
[0203] The copolymer described above is useful as an emulsifier for
water in oil (w/o) type emulsions, particularly where the oil
comprises a silicone and/or an organic oil. The copolymer may
provide an emulsion with low odor, i.e., lower odor than as
compared to emulsions containing silicone polyether emulsifiers.
The copolymer may also provide an emulsion which is nonirritating
to the skin, i.e., the a personal care product containing a safe
and effective amount of the emulsion containing the copolymer is
suitable for application to skin.
* * * * *